Monomers comprising at least one 4-(2-oxyethylidene)-1,3-dioxolan-2-one unit and use thereof

ABSTRACT

A compound of formula (I) 
     
       
         
         
             
             
         
       
     
     wherein R 1  is hydrogen or an organic radical of 1 to 100 carbon atoms, R 2 , R 3  are independently hydrogen or an organic radical of 1 to 100 carbons, Z is a single bond or a divalent organic group of 1 to 100 carbons, A is an (n+m)-valent organic group of 1 to 1 000 000 carbons, X is a single bond or a divalent organic group of 1 to 40 carbons, n is an integer from 1 to 1000, m is 0, 1, or 2, the sum of n+m being an integer from 2 to 1002. Such compounds are obtainable from specific 4-oxy-but-2-yn-1-ol derivatives, or used as intermediate(s), crosslinker(s), or monomer(s) in polymerization or oligomerization reactions, or for two-component compositions having such compound(s) and multifunctional hardener(s). Such compound(s) may be used to prepare polyunsaturated compounds, by reaction with an (oligo/poly)-functional nucleophile, or polymers.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a U.S. bypass continuation of InternationalApplication No. PCT/EP2019/061774, filed on May 8, 2019, published as WO2019/219469 A1 on Nov. 21, 2019, and claims benefit to EuropeanApplication No. 18 173 232.2, filed on May 18, 2018, each of which isincorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to a compound of formula (I)

wherein R¹ is hydrogen or an organic radical having from 1 to 100 carbonatoms, R², R³ independently of one another are hydrogen or an organicradical having from 1 to 100 carbon atoms, Z is a chemical single bondor a divalent organic group having from 1 to 100 carbon atoms, A is a(n+m)-valent organic group having from 1 to 1 000 000 carbon atoms, X isa chemical single bond or a divalent organic group having from 1 to 40carbon atoms, n is an integer from 1 to 1000, m is 0, 1 or 2, whereinthe sum of n+m is an integer from 2 to 1002.

The present invention further relates to processes for preparingcompounds of formula (I), to specific 4-oxy-but-2-yn-1-ol derivatives asstarting materials for the preparation of compounds of formula (I), tothe use of the compound of formula (I) as intermediate or crosslinker oras monomer in polymerization reactions or in oligomerization reactions,to two-component compositions comprising as a first component at leastone compound of formula (I), as a second component at least onemultifunctional hardener, to polymers formed from one or more monomers,wherein at least one monomer is a compound of formula (I) and to the useof any compound described before as an intermediate for the preparationof polyunsaturated compounds by reacting a (oligo/poly)-functionalnucleophile with a compound of formula (I). The reaction product can besubsequently applied to further curing (e.g. radical induced curing).

BACKGROUND OF THE INVENTION

Exo vinylene carbonates are valuable compounds, especially for the useas monomers in polymer applications as described in WO 2015/164692 A1,WO 2013/144299 A1, WO 2015/039807 and WO 2011/157671 A1.

For polymer applications on a larger scale, it is desirable to produceexo vinylene carbonates based on starting materials which are cheap andeasily available. The most atom-efficient access to exo vinylenecarbonates is via the carboxylation of 4-oxy-but-2-yn-1-ol derivativeswith CO₂.

The 4-oxy-but-2-yn-1-ol derivative, which is industrially produced onthe largest scale, is 1,4-butynediol. Therefore, this4-oxy-but-2-yn-1-ol derivative is also the most available and cheapest4-oxy-but-2-yn-1-ol derivative. Therefore, it is highly attractive touse 4-oxy-but-2-yn-1-ol derivatives, which are based on the readilyavailable 1,4-butynediol, as starting materials for the production ofexo vinylene carbonates, which can be used in polymer applications.

The exo vinylene carbonates with substituents in the 4,4-position areavailable via the reaction of secondary or tertiary propargylic alcoholswith CO₂ using different catalysts like metals or bases.

None of the protocols, which are described in the literature, like theSilver-, Copper-, Cobalt- or guanidine catalyzed cyclisation could untilnow be applied to the conversion of simple primary propargylic alcoholswith CO₂ towards the simple Exo-vinylene carbonates with two hydrogensin the 4,4-positions.

Accordingly, an aspect of the invention provides new compoundscomprising at least one 4-(2-oxyethylidene)-1,3-dioxolan-2-one, whichcan be used as monomers in polymer applications and which are based oneasily accessible 4-oxy-but-2-yn-1-ol derivatives, preferably based on1,4-butynediol. Another aspect of the invention provides economicprocesses for producing said compounds, which can be used asintermediates, as crosslinkers or as monomers in polymer applications,wherein the starting materials are based on easily accessible4-oxy-but-2-yn-1-ol derivatives, preferably based on 1,4-butynediol.

BRIEF SUMMARY OF THE INVENTION

One or more problems described above may be addressed by a compound offormula (I)

wherein

-   R¹ is hydrogen or an organic radical having from 1 to 100,    preferably 1 to 40 carbon atoms, preferably hydrogen, C₁-C₄ alkyl,    CH₂COOR⁴, phenyl or phenyl-C₁-C₄ alkyl;-   R², R³ independently of one another are hydrogen or an organic    radical having from 1 to 100, preferably 1 to 40 carbon atoms,    preferably hydrogen or C₁-C₄ alkyl or one of the radicals, R² or R³,    may be COOR⁴ or CH₂COOR⁴,-   R⁴ where present is hydrogen or an organic radical having from 1 to    100, preferably 1 to 40 carbon atoms, preferably hydrogen or C₁-C₆,-   Z is a chemical single bond or a divalent organic group having from    1 to 100, preferably 1 to 40 carbon atoms,-   A is a (n+m)-valent organic group having from 1 to 1 000 000 carbon    atoms,-   X is a chemical single bond or a divalent organic group having from    1 to 40 carbon atoms,-   n is an integer from 1 to 1000,-   m is 0, 1 or 2,-   wherein the sum of n+m is an integer from 2 to 1002.

DETAILED DESCRIPTION OF THE INVENTION

The substituents according to the present invention are, unlessrestricted further, defined as follows:

The term “organic radical having from 1 to 100 carbon atoms” or “organicradical having from 1 to 40 carbon atoms” as used in the present textrefers to, for example, C₁-C₄₀-alkyl radicals, C₁-C₁₀-fluoroalkylradicals, C₁-C₁₂-alkoxy radicals, saturated C₃-C₂₀-heterocyclicradicals, C₆-C₄₀-aryl radicals, C₂-C₄₀-heteroaromatic radicals,C₆-C₁₀-fluoroaryl radicals, C₆-C₁₀-aryloxy radicals, silyl radicalshaving from 3 to 24 carbon atoms, C₂-C₂₀-alkenyl radicals,C₂-C₂₀-alkynyl radicals, C₇-C₄₀-arylalkyl radicals or C₈-C₄₀-arylalkenylradicals. An organic radical is in each case derived from an organiccompound. Thus, the organic compound methanol can in principle give riseto three different organic radicals having one carbon atom, namelymethyl (H₃C—), methoxy (H₃C—O—) and hydroxymethyl (HOC(H₂)—). Therefore,the term “organic radical having from 1 to 100 carbon atoms” comprisesbeside alkoxy radicals for example also dialkylamino radicals,monoalkylamino radicals or alkylthio radicals.

In the present description, the term radical is used interchangeablywith the term group, when defining the variables R^(x) in the presentedformulas.

The term “alkyl” as used in the present text encompasses linear orsingly or multiply branched saturated hydrocarbons which can also becyclic. Preference is given to a C₁-C₁₈-alkyl radical such as methyl,ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl,n-decyl, cyclopentyl, cyclohexyl, isopropyl, isobutyl, isopentyl,isohexyl, sec-butyl or tert-butyl.

The term “alkenyl” as used in the present text encompasses linear orsingly or multiply branched hydrocarbons having one or more C-C doublebonds which can be cumulated or alternating.

The term “saturated heterocyclic radical” as used in the present textrefers to, for example, monocyclic or polycyclic, substituted orunsubstituted aliphatic or partially unsaturated hydrocarbon radicals inwhich one or more carbon atoms, CH groups and/or CH₂ groups have beenreplaced by heteroatoms which are preferably selected from the groupconsisting of the elements O, S, N and P. Preferred examples ofsubstituted or unsubstituted saturated heterocyclic radicals arepyrrolidinyl, imidazolidinyl, pyrazolidinyl, piperidyl, piperazinyl,morpholinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothiophenyland the like, and also methyl-, ethyl-, propyl-, isopropyl- andtert-butyl-substituted derivatives thereof.

The term “aryl” as used in the present text refers to, for example,aromatic and optionally fused polyaromatic hydrocarbon radicals whichmay be monosubstituted or polysubstituted by linear or branchedC₁-C₁₈-alkyl, C₁-C₁₈-alkoxy, C₂-C₁₀-alkenyl or halogen, in particularfluorine. Preferred examples of substituted and unsubstituted arylradicals are, in particular, phenyl, pentafluorophenyl, 4-methylphenyl,4-ethylphenyl, 4-n-propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl,4-methoxyphenyl, 1-naphthyl, 9-anthryl, 9-phenanthryl,3,5-dimethylphenyl, 3,5-di-tert-butylphenyl or 4-trifluoromethylphenyl.

The term “heteroaromatic radical” as used in the present text refers to,for example, aromatic hydrocarbon radicals in which one or more carbonatoms or CH groups have been replaced by nitrogen, phosphorus, oxygen orsulfur atoms or combinations thereof. These may, like the aryl radicals,optionally be monosubstituted or polysubstituted by linear or branchedC₁-C₁₈-alkyl, C₂-C₁₀-alkenyl or halogen, in particular fluorine.Preferred examples are furyl, thienyl, pyrrolyl, pyridyl, pyrazolyl,imidazolyl, oxazolyl, thiazolyl, pyrimidinyl, pyrazinyl and the like,and also methyl-, ethyl-, propyl-, isopropyl- and tert-butyl-substitutedderivatives thereof.

The term “arylalkyl” as used in the present text refers to, for example,aryl-comprising substituents whose aryl radical is linked via an alkylchain to the remainder of the molecule. Preferred examples are benzyl,substituted benzyl, phenethyl, substituted phenethyl and the like.

The terms fluoroalkyl and fluoroaryl mean that at least one hydrogenatom, preferably more than one and at most all hydrogen atoms, of thecorresponding radical have been replaced by fluorine atoms. Examples ofpreferred fluorine-comprising radicals are trifluoromethyl,2,2,2-trifluoroethyl, pentafluorophenyl, 4-trifluoromethylphenyl,4-perfluoro-tert-butylphenyl and the like.

With regard to preferred embodiments of the invention, the radicals,groups or variables R¹, R², R³, R⁴, Z, A, n and m in the compounds ofthe formula (I) preferably each independently have one or more or all ofthe following definitions:

R¹ is hydrogen or an organic radical having from 1 to 100, preferably 1to 40 carbon atoms. Preferably R¹ is hydrogen, C₁-C₄ alkyl, such asmethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or sec.-butyl, or R¹is CH₂COOR⁴, phenyl or phenyl-C₁-C₄ alkyl. Particularly preferably R¹ ishydrogen or methyl.

R² is hydrogen or an organic radical having from 1 to 100, preferably 1to 40 carbon atoms. Preferably R² is hydrogen, C₁-C₄ alkyl, such asmethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or sec.-butyl, or R²is COOR⁴ or CH₂COOR⁴. Particularly preferably R² is hydrogen.

R³ is hydrogen or an organic radical having from 1 to 100, preferably 1to 40 carbon atoms. Preferably R³ is hydrogen, C₁-C₄ alkyl, such asmethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or sec.-butyl, or R³is COOR⁴ or CH₂COOR⁴. Particularly preferably R³ is hydrogen.

R⁴, if present, is hydrogen or an organic radical having from 1 to 100,preferably 1 to 40 carbon atoms. Preferably R⁴ is hydrogen or C₁-C₆alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl,sec.-butyl, n-pentyl, n-hexyl or cyclohexyl. Particularly preferably R⁴is C₁-C₄ alkyl.

Z is a chemical single bond or a divalent organic group having from 1 to100, preferably 1 to 40 carbon atoms. Preferably Z is a chemical singlebond or a divalent organic group selected from the group of elementsconsisting of —CH₂—, —PO₂—, —SO₂—, —C(═O)—, —C(═O)—O— and —C(═O)—N(R⁵)—,where R⁵ is hydrogen, C₁-C₄ alkyl or phenyl, preferably hydrogen.

A is a (n+m)-valent organic group having from 1 to 1 000 000 carbonatoms. Preferably the (n+m)-valent organic group A is derived from anorganic compound selected from the group consisting of C₁-C₄₀-alkanes,C₁-C₄₀-alkenes, saturated C₃-C₁₀₀-heterocycles, aromaticC₆-C₄₀-hydrocarbons, C₂-C₄₀-heteroarenes, C₇-C₄₀-arylalkanes andC₈-C₄₀-arylalkenes, wherein in each member of the group, one or morehydrogen atoms can be substituted by halogens, OH, —NR⁶ ₂ or —CN and oneor more CH₂-groups can be substituted by —O—, —S—, —N(R⁶)—, PO₂—, —SO₂—,—C(═O)—, —C(═O)—O— or —C(═O)—N(R⁵)—, wherein R⁶ is hydrogen, C₁-C₄ alkylor phenyl, and from polymers, which are selected from the group ofpolymers consisting of poly(meth) acrylates, polyesters, polyurethanes,polyethers, polyamides, polycarbonates and polyolefins.

X is a chemical single bond or a divalent organic group having from 1 to40 carbon atoms. Preferably X is a chemical single bond or a divalentorganic group selected from the group of elements consisting of —C(═O)—,—O—C(═O)— and —N(R⁵)—C(═O)—, where R⁵ is hydrogen, C₁-C₄ alkyl orphenyl, preferably hydrogen.

The variable n is an integer from 1 to 1000. Preferably n is 1, 2, 3, 4,5 or 6, more preferably 2, 3 or 4, even more preferably 2 or 3, inparticular 2.

The variable m is 0, 1 or 2, preferably 0 or 1, in particular 0.

The sum of n+m is an integer from 2 to 1002. Preferably the sum of n+mis 2, 3, 4, 5 or 6, more preferably 2 or 3, in particular 2.

In cases wherein the variable n is 2 or more, the two or more Z groupscan be all identical or can be independently from each other different.Preferably, two or more Z groups are identical, disregarding differentisotopes of a chemical element in an organic group. In the context ofthe present invention, the organic groups —¹²C(═O)— and —¹³C(═O)— areconsidered to be identical.

In cases wherein m is two, the two X groups can be also identical ordifferent.

An inventive compound of formula (I) may be characterized in that

-   R¹ is hydrogen, C₁-C₄ alkyl, CH₂COOR⁴, phenyl or phenyl-C₁-C₄ alkyl;-   R², R³ independently of one another are hydrogen or C₁-C₄ alkyl or    one of the radicals, R² or R³, may be COOR⁴ or CH₂COOR⁴,-   R⁴ where present is hydrogen or C₁-C₆ alkyl.

An inventive compound of formula (I) may be characterized in that

-   Z is a chemical single bond or a divalent organic group selected    from the group of elements consisting of —CH₂—, —PO₂—, —SO₂—,    —C(═O)—, —C(═O)—O— and —C(═O)—N(R⁵)—, where R⁵ is hydrogen, C₁-C₄    alkyl or phenyl, preferably hydrogen.

An inventive compound of formula (I) may be characterized in that

-   X is chemical single bond or a divalent organic group selected from    the group of elements consisting of —C(═O)—, —O—C(═O)— and    -   —N(R⁵)—C(═O)—, where R⁵ is hydrogen, C₁-C₄ alkyl or phenyl,        preferably hydrogen.

An inventive compound of formula (I) may be characterized in that

-   n is 1, 2, 3, 4, 5 or 6, preferably 2, 3 or 4, more preferably 2 or    3, in particular 2,-   m is 0, 1 or 2, preferably 0 or 1, in particular 0,-   wherein the sum of n+m is 2, 3, 4, 5 or 6, preferably 2 or 3, in    particular 2.

An inventive compound of formula (I) may be characterized in that the(n+m)-valent organic group A is derived from an organic compoundselected from the group consisting of C₁-C₄₀-alkanes, C₁-C₄₀-alkenes,saturated C₃-C₁₀₀-heterocycles, aromatic C₆-C₄₀-hydrocarbons,C₂-C₄₀-heteroarenes, C₇-C₄₀-arylalkanes and C₈-C₄₀-arylalkenes, whereinin each member of the group, one or more hydrogen atoms can besubstituted by halogens, —NR⁶ ₂, CN or OH and one or more CH₂-groups canbe substituted by —O—, —S—, —N(R⁶)—, PO₂—, —SO₂—, —C(═O)—, —C(═O)—O— or—C(═O)—N(R⁵)—, wherein R⁵ is hydrogen, C₁-C₄ alkyl or phenyl, preferablyhydrogen and wherein R⁶ is hydrogen, C₁-C₄ alkyl or phenyl, and frompolymers, which are selected from the group of polymers consisting ofpoly(meth) acrylates, polyesters, polyurethanes, polyethers, polyhydroxyethers, polyamides, polycarbonates and polyolefins.

An inventive compound of formula (I) may be characterized in that

-   R¹ is hydrogen, C₁-C₄ alkyl, CH₂COOR⁴, phenyl or phenyl-C₁-C₄ alkyl,    preferably R¹ is hydrogen or methyl,-   R², R³ independently of one another are hydrogen or C₁-C₄ alkyl or    one of the radicals, R² or R³, may be COOR⁴ or CH₂COOR⁴, preferably    R², R³ are both hydrogen,-   R⁴ where present is hydrogen or C₁-C₆ alkyl, preferably R⁴ is C₁-C₄    alkyl,-   Z is a chemical single bond or a divalent organic group selected    from the group of elements consisting of —CH₂—, —PO₂—, —SO₂—,    —C(═O)—, —C(═O)—O— and —C(═O)—N(R⁵)—,-   A is a divalent organic group derived from an organic compound    selected from the group consisting of C₁-C₄₀-alkanes,    C₁-C₄₀-alkenes, saturated C₃-C₂₀-heterocycles, aromatic    C₆-C₄₀-hydrocarbons, C₂-C₄₀-heteroarenes, C₇-C₄₀-arylalkanes and    C₈-C₄₀-arylalkenes, wherein in each member of the group, one or more    hydrogen atoms can be substituted by halogens, OH, —NR⁶ ₂ or —CN,    and one or more CH₂-groups can be substituted by —O—, —S—, —N(R⁶)—,    PO₂—, —SO₂—, —C(═O)—, —C(═O)—O— or —C(═O)—N(R⁵)—,-   X is chemical single bond or a divalent organic group selected from    the group of elements consisting of —C(═O)—, —O—C(═O)— and    —N(R⁵)—C(═O)—,    -   wherein R⁵ is hydrogen, C₁-C₄ alkyl or phenyl, preferably        hydrogen, and wherein R⁶ is hydrogen, C₁-C₄ alkyl or phenyl,-   n is 1,-   m is 1.

Compounds of formula (I), wherein m is 0 and n is 2, 3, 4, 5 or 6,preferably 2, 3 or 4, more preferably 2 or 3, in particular 2, are alsovaluable monomers in polymerization reactions or as intermediate in thereaction with nucleophiles, in particular, as monomers for the formationof poly(keto urethanes), poly(keto carbonates), poly(ketothiocarbonates, poly(keto ethers) or polymers comprising a mixture ofthe functional groups selected from the group consisting of ketourethanes, keto carbonates, keto thiocarbonates and keto ethers.

Compounds of formula (I), wherein m is 1 or 2, preferably 1, and n=1 arealso valuable as monomer for the formation of polyunsaturated urethanes,polyunsaturated carbonates, polyunsaturated thiocarbonates, or polymerscomprising a mixture of the functional groups selected from the groupconsisting of unsaturated urethanes, unsaturated carbonates, unsaturatedthiocarbonates.

An inventive compound of formula (I) may be characterized in that

-   n is 2, 3, 4, 5 or 6, preferably 2, 3 or 4, more preferably 2 or 3,    in particular 2,-   m is 0,-   Z is a chemical single bond or a divalent organic group selected    from the group of elements consisting of —CH₂—, —PO₂—, —SO₂—,    —C(═O)—, —C(═O)—O— and —C(═O)—N(R⁵)—,-   A is a n-valent organic group, which is derived from an organic    compound selected from the group consisting of C₁-C₄₀-alkanes,    C₁-C₄₀-alkenes, saturated C₃-C₁₀₀-heterocycles, aromatic    C₆-C₄₀-hydrocarbons, C₂-C₄₀-heteroarenes, C₇-C₄₀-arylalkanes and    C₈-C₄₀-arylalkenes, wherein in each member of the group, one or more    hydrogen atoms can be substituted by halogens, OH, —NR⁶ ₂ or —CN and    one or more CH₂-groups can be substituted by —O—, —S—, —N(R⁶)—,    PO₂—, —SO₂—, —C(═O)—, —C(═O)—O— or —C(═O)—N(R⁵)—, and from polymers,    which are selected from the group of polymers consisting of    poly(meth) acrylates, polyesters, polyurethanes, polyethers,    polyamides, polycarbonates and polyolefins, wherein R⁵ is hydrogen,    C₁-C₄ alkyl or phenyl, preferably hydrogen, and wherein R⁶ is    hydrogen, C₁-C₄ alkyl or phenyl.

An inventive compound of formula (I) may be characterized in that

-   n is 2, 3 or 4, more preferably 2 or 3, in particular 2,-   m is 0,-   Z is a chemical single bond or a divalent organic group selected    from the group of elements consisting of —CH₂—, —C(═O)—, —C(═O)—O—    and —C(═O)—N(R⁵)—,-   A is a n-valent organic group, which is derived from an organic    compound selected from the group consisting of C₁-C₁₂-alkanes,    saturated C₃-C₆₀-heterocycles, aromatic C₆-C₄₀-hydrocarbons,    C₂-C₄₀-heteroarenes and C₇-C₃₀-arylalkanes, wherein in each member    of the group, one or more hydrogen atoms can be substituted by    halogens, OH, —NR⁶ ₂ or —CN and one or more CH₂-groups can be    substituted by —O—, —S—, —N(R⁶)—, PO₂—, —SO₂—, —C(═O)—, —C(═O)—O— or    —C(═O)—N(R⁵)—, and from polymers, which are selected from the group    of polymers consisting of poly(meth) acrylates, polyesters,    polyurethanes, polyethers, polyamides, polycarbonates and    polyolefins,    -   wherein R⁵ is hydrogen, C₁-C₄ alkyl or phenyl, preferably        hydrogen, and    -   wherein R⁶ is C₁-C₄ hydrogen, alkyl or phenyl.

In one embodiment of the present invention, the inventive compound offormula (I) is characterized in that the compound of formula (I) isselected from the group consisting of

The compounds of formula (I) comprise one or more functional groups ofthe formula (Ia),

wherein the functional group of the formula (Ia) stands for therespective cis-isomer or trans-isomer or in case that more than onefunctional group of the formula (Ia) are present in the compound offormula (I), formula (Ia) stands also for a mixture of said cis-transisomers.

The inventive compounds of formula (I) can be prepared from startingmaterials which are based on easily accessible 4-oxy-but-2-yn-1-olderivatives, preferably based on 1,4-butynediol, wherein the functionalgroup of the formula (Ia) is obtained by a reaction of the functionalgroup of formula (IIa), wherein Z and # are defined as described above,with carbon dioxide in the presence of a transition metal catalysts.

Alternatively, compounds of formula (I), wherein m is 1 or 2, preferably1, can be polymerized, oligomerized or dimerized by a reaction of theC═C double bond of the functional group of formula (Ib),

wherein R¹, R², R³ and X have the same meaning as in formula (I) asdescribed above, by forming a new compound of formula (I), wherein m is0. Examples of suitable reactions of the C═C double bond of thefunctional group of formula (Ib) are radical polymerization oroligomerization reaction, Diels-Alder-reaction or thiol-ene reaction.Alternatively, reaction with amines could lead to nucleophilic ringopening as well as Michael-type addition towards the double bond(aza-Michael).

Such polymers, oligomers or dimers of formula (I) have a high reactivitycompared to compounds having functional groups F from the group of thealiphatic hydroxyl groups, primary and secondary amino groups, phosphinegroups, phosphonate groups and mercaptan groups, without having thedisadvantages associated with isocyanates. They are thereforeparticularly suitable as a replacement for polyfunctional isocyanates innumerous applications, especially for 2K binders as described in WO2013/144299 A1, whereby catalysts may be required for the activation ofsome functional groups F like activation of hydroxy groups with amineslike 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

A further aspect of the invention is a process for preparing a compoundof formula (I) as described above

comprising the process step:

-   a) reacting a 4-oxy-but-2-yn-1-ol derivative of formula (II)

wherein R¹, R², R³, Z, A, X, n and m have the same meaning as describedabove, with carbon dioxide in the presence of at least one transitionmetal catalyst TMC1, which comprises a transition metal selected frommetals of groups 10, 11 and 12 of the periodic table of the elementsaccording to IUPAC and at least one bulky ligand selected from the groupof ligands consisting of compounds of formula (III) and compounds offormula (IV)

wherein

-   D is P, As or Sb,-   R⁷ is an organic radical having from 1 to 40 carbon atoms,-   R⁸, R⁹ are identical or different, and are each an organic radical    having from 1 to 40 carbon atoms, and,-   R¹⁰ is an organic radical having from 1 to 40 carbon atoms or is    identical to R⁷, and-   T is a divalent bridging group selected from —CR¹²═CR¹³—, —CR¹²═N—,    —CR¹²R¹⁴—CR¹³R¹⁵— and —CR¹²R¹⁴—CR¹³R¹⁵—CR¹⁶R¹⁷—, wherein R¹², R¹³,    R¹⁴, R¹⁵, R¹⁶ and R¹⁷ are independently from each other hydrogen or    as defined as R¹⁰ or two adjacent radicals R¹² and R¹³ and/or R¹⁵    and R¹⁶ together with the atoms connecting them form a monocyclic or    polycyclic, substituted or unsubstituted, aliphatic or aromatic ring    system which has from 4 to 40 carbon atoms and can also comprise at    least one heteroatom selected from the group consisting of the    elements Si, Ge, N, P, O and S.

The inventive process may be characterized in that

-   D is P,-   R⁷ is a C₃ to C₄₀ cycloalkyl radical, a C₂ to C₄₀ heterocycloalkyl    radical, a C₆ to C₄₀ aryl radical or a C₂ to C₄₀ heteroaromatic    radical, preferably a C₆ to C₄₀ aryl radical or a C₂ to C₄₀    heteroaromatic radical, wherein R⁷ is substituted in at least one of    the two ortho positions relative to P or N with a radical R¹¹, which    is an organic radical having from 1 to 40 carbon atoms, a halogen,    in particular Cl or Br, hydroxy, SO₃H or nitro or wherein R¹¹    together with an adjacent radical substituting R⁷ in the meta    position forms together with the atoms connecting them a monocyclic    or polycyclic, substituted or unsubstituted, aliphatic or aromatic    ring system, which has from 4 to 40 carbon atoms and can also    comprise at least one heteroatom selected from the group consisting    of the elements Si, Ge, N, P, O and S, preferably N and O,-   R⁸, R⁹, R¹⁰ and T are defined as described above.

In the process of the invention, the 4-oxy-but-2-yn-1-ol derivative offormula (II) is reacted with carbon dioxide in the presence of at leastone transition metal catalyst TMC1. Transition metal catalyst TMC1comprises a transition metal selected from metals of groups 10, 11 and12 of the periodic table of the elements according to IUPAC, such as Ni,Pd, Pt, Cu, Ag, Au, Zn, Cd and Hg, preferably selected from Cu, Ag andAu, more preferably selected from Cu or Ag, in particular Ag.

The inventive process may be characterized in that the transition metalof transition metal catalyst TMC1 is Ag

The transition metal catalyst TMC1 of the process of the invention canbe employed in the form of a preformed metal complex which comprises atransition metal and at least one bulky ligand selected from the groupof ligands consisting of compounds of formula (III) and compounds offormula (IV), preferably compounds of formula (III), as shown above.Alternatively, the transition metal catalyst TMC1 is formed in situ inthe reaction medium by combining a metal compound, herein also termedpre-catalyst, which does not comprise any bulky ligand, with one or moresuitable bulky ligand to form a catalytically active metal complex, thetransition metal catalyst TMC1, in the reaction medium. In case thebulky ligand is a N-heterocyclic carbene ligand (NHC-ligand) of formula(IV), it is also possible that the transition metal catalyst TMC1 isformed in situ in the reaction medium by combining a pre-catalyst withone or more NHC-precursor, in particular the protonated form of aNHC-ligand, which is in situ converted to the corresponding NHC-ligandof formula (IV), to form a catalytically active metal complex in thereaction medium.

The inventive process may be characterized in that the transition metalcatalyst TMC1 is prepared in situ by using a transition metal compound,which does not comprise any bulky ligand, the compound of formula (III)or formula (IV) as bulky ligand or the protonated form of the compoundof formula (IV) represented by formula (V),

wherein R⁷, R¹⁰ and T are defined as described above and X⁻ is an anionequivalent, together with a base.

Suitable bases for deprotonating the protonated form of different NHCligands according to formula (V) are described by de Frémont et al.,Coordination Chemistry Reviews 253 (2009) 876 to 881. The deprotonationof the protonated forms of NHC ligands can be carried out in ammonia orin non-protic solvents such as THF or ethers. The deprotonation requiresanhydrous conditions and the use of strong bases, with pK_(a) valuesabove 14. Usually, potassium or sodium hydride with a catalytic amountof tert-butoxide is employed, but tert-butoxide itself, lithium aluminumhydride, n-butyllithium, MeLi, t-BuLi, potassium hexamethyldisilazide(KHMDS) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) are also efficientalternatives.

Suitable pre-catalysts are selected from neutral metal complexes, oxidesand salts of metals of groups 10, 11 and 12 of the periodic table of theelements. Preferred pre-catalysts are selected from metal complexes,oxides and salts of copper, silver and gold, in particular silver.

Silver compounds that are useful as pre-catalyst are, for exampleAg(OAc), AgF, AgNO₃, silver trifluoroacetate, Ag₂O, Ag₂CO₃.

The inventive process may be characterized in that the transition metalcompound, also called pre-catalyst, is selected from AgOAc, AgF, Ag₂Oand Ag₂CO₃.

In addition to the transition metal, the transition metal catalyst TMC1comprises at least one bulky ligand selected from the group of ligandsconsisting of compounds of formula (III) and compounds of formula (IV,preferably compounds of formula (III).

In case the bulky ligand is a compound of formula (III),

the variables are preferably defined as follows:

-   D is P, As or Sb, preferably P or As, in particular P,-   R⁷ is an organic radical having from 1 to 40 carbon atoms,    preferably from 2 to 40 carbon atoms, preferably comprising at least    one cyclic ring,    -   more preferably R⁷ is a C₃ to C₄₀ cycloalkyl radical, a C₂ to        C₄₀ heterocycloalkyl radical, a C6 to C₄₀ aryl radical, a C₂ to        C₄₀ heteroaromatic radical, a C₃ to C₄₀ cycloalkoxy radical, a        C₂ to C₄₀ heterocycloalkoxy radical, a C₆ to C₄₀ aryloxy        radical, a C₂ to C₄₀ hetaryloxy radical,    -   even more preferably R⁷ is a C₃ to C₄₀ cycloalkyl radical, a C₂        to C₄₀ heterocycloalkyl radical, a C₆ to C₄₀ aryl radical or a        C₂ to C₄₀ heteroaromatic radical, preferably a C₆ to C₄₀ aryl        radical or a C₂ to C₄₀ heteroaromatic radical, wherein R⁷ is        substituted in at least one of the two ortho positions relative        to D with a radical R¹¹, which is an organic radical having from        1 to 40 carbon atoms, preferably a C₆ to C₄₀ aryl radical, a C₁        to C₁₀ alkoxy radical or a C₂ to C₁₂ dialkyl amino radical or        wherein R¹¹ together with an adjacent radical substituting R⁷ in        the meta position forms together with the atoms connecting them        a monocyclic or polycyclic, substituted or unsubstituted,        aliphatic or aromatic ring system, which has from 4 to 40 carbon        atoms and can also comprise at least one heteroatom selected        from the group consisting of the elements Si, Ge, N, P, O and S,        preferably N, O and S, and    -   R⁸, R⁹ are identical or different, preferably identical, and are        each an organic radical having from 1 to 40 carbon atoms,        preferably C₃ to C₂₀ cyclic or acyclic alkyl, in particular        tert.-butyl or cyclohexyl, or C₆ to C₁₄ aryl, in particular        phenyl.

In case the bulky ligand is a compound of formula (IV),

the variables are preferably defined as follows:

-   R⁷ is an organic radical having from 1 to 40 carbon atoms,    preferably from 2 to 40 carbon atoms, preferably comprising at least    one cyclic ring,    -   more preferably R⁷ is a C₆ to C₄₀ aryl radical or a C₂ to C₄₀        heteroaromatic radical, preferably wherein R⁷ is substituted in        at least one of the two ortho positions relative to N with a        radical R¹¹, which is an organic radical having from 1 to 40        carbon atoms, preferably a C₁ to C₁₀ alkyl radical, in        particular isopropyl,-   R¹⁰ is an organic radical having from 1 to 40 carbon atoms or is    identical to R⁷, preferably R¹⁰ is identical to R⁷, and-   T is a divalent bridging group selected from —CR¹²═CR¹³—, —CR¹²═N—,    —CR¹²R¹⁴—CR¹³R¹⁵— and —CR¹²R¹⁴—CR¹³R¹⁵—CR¹⁶R¹⁷—, preferably    —CR¹²═CR¹³— and —CR¹²R¹⁴—CR¹³R¹⁵—, wherein R¹², R¹³, R¹⁴, R¹⁵, R¹⁶    and R¹⁷ are independently from each other hydrogen or as defined as    R¹⁰, preferably hydrogen, or two adjacent radicals R¹² and R¹³    and/or R¹⁵ and R¹⁶ together with the atoms connecting them form a    monocyclic or polycyclic, substituted or unsubstituted, aliphatic or    aromatic ring system which has from 4 to 40 carbon atoms and can    also comprise at least one heteroatom selected from the group    consisting of the elements Si, Ge, N, P, O and S

The inventive process may be characterized in that the bulky ligand is acompound of formula (III).

The inventive process may be characterized in that the bulky ligand is acompound of formula (III)

wherein the variables are defined as follows:

-   D is P,-   R⁷ is a C₆ to C₄₀ aryl radical or a C₂ to C₄₀ heteroaromatic    radical, wherein R⁷ is substituted in at least one of the two ortho    positions relative to D with a radical R¹¹, which is a C₆ to C₄₀    aryl radical, a C₁ to C₁₀ alkoxy radical, in particular methoxy,    ethoxy, isopropoxy or cyclohexyloxy, or a C₂ to C₁₂ dialkyl amino    radical, in particular dimethyl amino, diethyl amino, di-isopropyl    amino, N-morpholinyl or N-piperidyl, or wherein R¹¹ together with an    adjacent radical substituting R⁷ in the meta position forms together    with the atoms connecting them a monocyclic or polycyclic,    substituted or unsubstituted, aliphatic or aromatic ring system,    which has from 4 to 40 carbon atoms and can also comprise at least    one heteroatom selected from the group consisting of the elements    Si, Ge, N, P, O and S, preferably N, O and S, and-   R⁸, R⁹ are identical or different, preferably identical, and are    each an organic radical having from 1 to 40 carbon atoms, preferably    C₃ to C₂₀ cyclic or acyclic alkyl, in particular tert.-butyl,    adamantyl or cyclohexyl, or C₆ to C₁₄ aryl, in particular phenyl.

The inventive process may be characterized in that the bulky ligand isselected from a compound of formulas A to P and mixtures thereof,preferably a compound of formulas A to D and mixtures thereof.

The molar ratio of the bulky ligand to the transition metal oftransition metal catalyst TMC1 can be varied in wide range. Preferablythe molar ratio of the bulky ligand to the transition metal is below 2.More preferably the ratio of the bulky ligand to the transition metal isin the range from 0.2 to 1.8, even more preferably in the range from 0.3to 1.5, in particular in the range from 0.4 to 1.2.

The inventive process may be characterized in that the molar ratio ofthe bulky ligand to the transition metal of transition metal catalystTMC1 is in the range from 0.4 to 1.2.

In the inventive process the amount of transition metal catalyst TMC1used in process step a) based on the amount of 4-oxy-but-2-yn-1-olderivative of formula (II) can be varied in a wide range. Usually thetransition metal catalyst TMC1 is used in a sub-stoichiometric amountrelative to the 4-oxy-but-2-yn-1-ol derivative of formula (II).Typically, the amount of transition metal catalyst TMC1 is not more than50 mol %, frequently not more than 20 mol % and in particular not morethan 10 mol % or not more than 5 mol %, based on the amount of4-oxy-but-2-yn-1-ol derivative of formula (II). An amount of transitionmetal catalyst TMC1 of from 0.001 to 50 mol %, frequently from 0.001 mol% to 20 mol % and in particular from 0.005 to 5 mol %, based on theamount the 4-oxy-but-2-yn-1-ol derivative of formula (II) is preferablyused in the process of the invention. Preference is given to using anamount of transition metal catalyst TMC1 of from 0.01 to 5 mol %. Allamounts of transition metal complex catalyst indicated are calculated astransition metal and based on the amount of 4-oxy-but-2-yn-1-olderivative.

The inventive process may be characterized in that the amount oftransition metal catalyst TMC1 used in process step a) based on theamount of 4-oxy-but-2-yn-1-ol derivative of formula (II) is in the rangefrom 0.005 to 5 mol %.

The reaction can principally be performed according to all processesknown to a person skilled in the art which are suitable for the reactionof primary propargylic alcohols with CO₂.

The CO₂ used for the carboxylation-cyclization reaction can be used inpure form or, if desired, also in the form of mixtures with other,preferably inert gases, such as nitrogen or argon. Preference is givento using CO₂ in undiluted form.

The reaction is typically carried at a CO₂ pressure in the range from0.1 to 200 bar, preferably in the range from 1 to 50 bar, morepreferably in the range from 1 to 40 bar.

The inventive process may be characterized in that the process step a)is performed at a pressure in the range from 1 to 50 bar, morepreferably in the range from 1 to 40 bar.

The reaction can principally be performed continuously,semi-continuously or discontinuously. Preference is given to acontinuous process.

The reaction can principally be performed in all reactors known by aperson in the art for this type of reaction and therefore, will selectthe reactors accordingly. Suitable reactors are described and reviewedin the relevant prior art, e.g. appropriate monographs and referenceworks such as mentioned in U.S. Pat. No. 6,639,114 B2, column 16, line45-49. Preferably, for the reaction an autoclave is employed which mayhave an internal stirrer and an internal lining such as a Teflon lining.

The composition obtained in the carboxylation-cyclization reaction ofthe present invention comprises a compound of formula (I), whichcomprises at least one 4-(2-oxyethylidene)-1,3-dioxolan-2-one unit.

Process step a) of the inventive process can be performed in a widetemperature range. Preferably process step a) is performed at atemperature in the range from 0° C. to 150° C. and particularlypreferably in the range from 10° C. to 80° C. Temperatures below 100° C.have surprisingly been found to be particularly advantageous.

The inventive process may be characterized in that the process step a)is performed at a temperature in the range from 0° C. to 100° C.,preferably in the range from 10° C. to 80° C.

The process of the invention can be carried out in the presence of asolvent. Suitable solvents are selected from aliphatic hydrocarbons,aromatic hydrocarbons, halogenated hydrocarbons, amides, ureas,nitriles, sulfoxides, sulfones, esters, carbonates, ethers, alcohols andmixtures thereof. Preferred solvents are

-   aliphatic hydrocarbons such as pentane, hexane, heptane, octane or    cyclohexane;-   aromatic hydrocarbons such as benzene, toluene, xylenes,    ethylbenzene, mesitylene or benzotrifluoride;-   halogenated hydrocarbons such as dichloromethane,-   amides such as dimethylformamide, diethylformamide,    N-methylpyrrolidone, N-ethylpyrrolidone or dimethylacetamide;-   ureas such as tetramethylurea, N,N-dimethylimidazolinone (DMI) and    N,N-dimethylpropyleneurea (DMPU);-   nitriles such as acetonitrile or propionitrile;-   sulfoxides such as dimethyl sulfoxide;-   sulfones such as sulfolane;-   esters such as methyl acetate, ethyl acetate, t-butyl acetate;-   carbonates such as diethyl carbonate, ethylene carbonate and    propylene carbonate; and-   ethers such as dioxane, tetrahydrofuran, diethyl ether, dibutyl    ether, methyl t-butyl ether, diisopropyl ether or diethylene glycol    dimethyl ether;

If desired, mixtures of two or more of the afore-mentioned solvents canalso be used.

Preference is given to using dichloromethane, acetone, dimethylformamideor acetonitrile as solvents.

The inventive process may be characterized in that the reaction iscarried out in the presence of a solvent selected from aliphatichydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, amides,ureas, nitriles, sulfoxides, sulfones, esters, carbonates, ethers,alcohols and mixtures thereof, preferably selected from dichloromethane,acetone, dimethylformamide or acetonitrile.

Alternatively, the process of the invention can be carried out in theabsence of any of the above-mentioned organic solvent, so-called neatconditions, preferably in the presence of liquid or supercritical carbondioxide, in particular in the presence of supercritical carbon dioxide.

Alternatively, the process of the invention can be carried out in thepresence of liquid or supercritical carbon dioxide, in particular in thepresence of supercritical carbon dioxide, which is mixed with one of theabove-mentioned organic solvent, so-called CO₂-expanded solvents.

The composition obtained in the carboxylation-cyclisation of theinvention comprises the compound of formula (I), which is a compoundcomprising at least one 4-(2-oxyethylidene)-1,3-dioxolan-2-one unit.

The work-up of the reaction mixture of the inventive process and theisolation of the compound of formula (I) are effected in a customarymanner, for example by filtration, an aqueous extractive work-up or by adistillation, for example under reduced pressure. The compound offormula (I) may be obtained in sufficient purity by applying suchmeasures or a combination thereof, obviating additional purificationsteps. Alternatively, further purification can be accomplished bymethods commonly used in the art, such as chromatography.

The inventive process may be characterized in that the compound offormula (I) is separated from the transition metal catalyst TMC1 afterprocess step a) via distillation, extraction, precipitation orchromatography.

The inventive process may be characterized in that the transition metalcatalyst TMC1 is recycled to the reaction step a) after the compound offormula (I) is removed via distillation, extraction, precipitation orchromatography.

Alternatively, the inventive compounds of formula (I) can be prepared byreacting 4-(2-hydroxyethylidene)-1,3-dioxolan-2-one (VIa) with anappropriate linker, which comprises one or more functional groupscapable to react with the hydroxy group of the alcohol of formula (VIa)to obtain a compound of formula (I).

The alcohol of formula (VIa), 4-(2-hydroxyethylidene)-1,3-dioxolan-2-oneis directly available by the reaction of 1,4-butynediol with carbondioxide in the presence of at least one transition metal catalyst TMC1as described in detail above or as described in EP application No17186136.2. Derivatives of the alcohol of formula (VIa) are easilyavailable, wherein the hydroxy group OH is substituted by anether-hydroxy group —O-J-OH, as subsequently explained.

A further aspect of the invention is a process for preparing a compoundof formula (I) as described above

comprising the process step:

-   b) reacting an alcohol of formula (VI)

-   -   with a compound of formula (VII)

-   -   wherein R¹, R², R³, A, X, n and m have the same meaning as in        formula I, and    -   wherein    -   J is a divalent organic group having from 1 to 100 carbon atoms,        preferably 1 to 40 carbon atoms,    -   Q is a functional group capable to react with the hydroxy group        of the alcohol of formula (VI) in an addition reaction under        formation of a —O-Q(-H)-A unit or Q is a leaving group        substituted by the oxygen of the hydroxy group of the alcohol of        formula (VI) under formation of H-Q, and    -   o is 0 or 1.

J is a divalent organic group having from 1 to 100 carbon atoms,preferably 1 to 40 carbon atoms. Preferably J is a divalent organicgroup derived from an organic compound selected from the groupconsisting of C₁-C₄₀-alkanes, C₁-C₄₀-alkenes, saturatedC₃-C₂₀-heterocycles, aromatic C₆-C₄₀-hydrocarbons, C₂-C₄₀-heteroarenes,C₇-C₄₀-arylalkanes and C₈-C₄₀-arylalkenes, wherein in each member of thegroup, one or more hydrogen atoms can be substituted by halogens, OH,—NR⁶ ₂ or —CN, and one or more CH₂-groups can be substituted by —O—,—S—, —N(R⁶)—, PO₂—, —SO₂—, —C(═O)—, —C(═O)—O— or —C(═O)—N(R⁵), whereinR⁵ is hydrogen, C₁-C₄ alkyl or phenyl, preferably hydrogen, and whereinR⁶ is hydrogen, C₁-C₄ alkyl or phenyl. More preferably, J is a divalentorganic group derived from an organic compound selected from the groupconsisting of C₁-C₄₀-alkanes, wherein one or more CH₂-groups can besubstituted by —O—.

Preferred, but not limiting examples of J are —CH₂—, —CH₂—CH₂—,—CH₂—C(MeH)—, —(CH₂)₄—, —(CH₂)₆—, —CH₂—C₆H₆—CH₂—, —(CH₂—O)₁₋₂₀—CH₂—,—(CH₂—CH₂—O)₁₋₂₀—CH₂—CH₂—, —(CH₂—C(MeH)—O)₁₋₂₀—CH₂—C(MeH)— or—((CH₂)₄—O—)₁₋₂₀—(CH₂)₄—, in particular —CH₂—CH₂—, —CH₂—C(MeH)—,—(CH₂)₄—, —(CH₂—CH₂—O)₁₋₃—CH₂—CH₂—, —(CH₂—C(MeH)—O)₁₋₃—CH₂—C(MeH)— or—((CH₂)₄—O—)₁₋₃—(CH₂)₄—. The index range 1-3 stands for the indices 1, 2or 3 and the index range 1-20 stands for the indices 1, 2, 3, 4, 5, 6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

Suitable functional groups Q, which are capable to react with a primaryor secondary hydroxy group of the fragment HO—CH₂— or HO—CH(Me)- and thecorresponding linkers of formula (VII) are known to a person skilled inthe art.

The inventive process may be characterized in that

-   Q is selected from the group of the functional groups consisting of    —N═C═O (or derivatives), 2-oxiranyl, —C═N—, C═C═O, halides,    preferably Cl, Br or I, and organic sulfonates, preferably tosylate,    mesylate, triflate or nonaflate, and OH, R^(a)C(═O)O, R^(a)O and    imidazole, where R^(a) is C₁-C₄ alkyl or substituted or    unsubstituted phenyl, preferably selected from the group of the    functional groups consisting of —N═C═O, Cl, Br and imidazole.

The inventive process may be characterized in that the compound offormula (VII) is selected from the group of compounds consisting of

A further aspect of the invention is a compound of formula (II)

wherein R¹, R², R³, Z, A, X, n and m have the same meaning as in formulaI as described above.

Compounds of formula (II) are available by reacting 1,4-butynediol withan appropriate linker, preferably, a compound of formula (VII) asdescribed above. Preferably 1,4-butynediol is mono-functionalized toobtain the compound of formula (II).

Compounds of formula (VII) comprise one or more functional groups Q,which are capable to react with one of the two hydroxy group of1,4-butynediol to obtain the compound of formula (II). Examples of suchfunctional groups are a polymerizable olefin function, phosgene orderivatives, CDI, carbonates, chloroformiate, a carboxylic acid functionand derivates thereof such as an ester, an anhydride function, a keteneor acid chloride function, further an alcohol function, a protectedamine function e.g. an imine, an isocyanate function (or derivatives),an alkylcarbonate function, an uretdione function, an alkyne function,an vinylether function, an epoxy-function, an diimide function, a cycliccarbonate function, vinylene-1,3 dicarbonyl function or another cylicexo-vinylencarbonate function or aldehydes. In case of another exovinylene carbonate unit, it's preferred to install this group also byusing the above mentioned catalytic system and therefor substrates withtwo 4-oxy-but-2-yn-1-ol derivative functions must be used as thesubstrate to obtain di-exo vinylene carbonates.

Non-limiting examples of compounds of formula (VII) are for example2,4-toluendiisocynate, 2,6-toluenediisocyante,1,6-hexamethylenediisocynate, adipic acid chloride, aromatic acidchlorides such as terephthaloyl chloride, di(m)ethylcarbonate,diphenylcarbonate, alkynes, mono- and difunctional Michael acceptorssuch as BDO-bis-(meth)acrylate, di(meth)acrylamides, (bis)maleides,divinylether, cyano acrylate, methylene malonate, phosgene, methacrylicacid anhydride, 2-(methacryloxy)ethyl isocyanate, maleic acid anhydride,succinic acid anhydride, bis(2-chloroethyle)ether,bis(2-chloroethyl)amine, 1,4-bis-chloromethylbenzene,1,4-bis-bromo-momethylbenzene, 1,2-bis-chloromethylbenzene,1,2-bis-bromo-momethylbenzene, 1,3-bis-chloromethylbenzene,1,3-bis-bromo-methylbenzene or 1,1-Carbonyldidimidazol. Furthermore,inorganic compounds such as silicates (e.g. via transesterification),sulfates (e.g. via transesterification or addition to divinyl sulfate),sulfonates, phosphates and phosphonates might be used as linker.

In one embodiment of the present invention, the inventive compound offormula (II) is characterized in that the compound of formula (II) isselected from the group consisting of

A further aspect of the invention is a process for preparing a compoundof formula (II) as described above comprising the process step:

-   c) reacting the diol 1,4-butynediol of formula (VIII)

-   -   with a compound of formula (VII)

-   -   wherein R¹, R², R³, A, X, n and m have the same meaning as in        formula I, and    -   wherein    -   Q is a functional group capable to react with the hydroxy group        of the alcohol of formula (VI) in an addition reaction under        formation of a —O-Q(-H)-A unit or Q is a leaving group        substituted by the oxygen of the hydroxy group of the alcohol of        formula (VI) under formation of H-Q.

Suitable functional groups Q, which are capable to react with a primaryhydroxy group of the fragment HO—CH₂— and the corresponding linkers offormula (VII) are known to a person skilled in the art and have beendescribed above.

A further aspect of the present invention is the use of 1,4but-2-in-diol for the preparation of compounds of formula (I),preferably for the preparation of compounds of formula (I) withoutprotecting any functional groups or without using any protectionchemistry for functional groups, which are well known to a personskilled in the art.

Alternatively, compounds of formula (II), wherein m is 1 or 2,preferably 1, can be polymerized, oligomerized or dimerized by areaction of the C═C double bond of the functional group of formula (Ib),

wherein R¹, R², R³ and X have the same meaning as in formula I asdescribed above, by forming a new compound of formula (II), wherein m is0. Examples of suitable reactions of the C═C double bond of thefunctional group of formula (Ib) are radical polymerization oroligomerization reaction, Diels-Alder-reaction or thiol-ene reaction.

Compounds of formula (II) can also be prepared in a multi-stepsynthesis, wherein the HO—CH₂— group of the functional group of formula(IIa) of the compound of formula (II),

wherein Z and # are defined as described above, is prepared in the finalstep from the corresponding functional group of formula (IIb).

The following scheme shows one possible example of this syntheticstrategy.

The inventive compounds of formula (I) can be used in the same way asthe related higher substituted, more complicated exo-vinylene carbonatesas described in the introduction.

Therefore, a further aspect of the present invention is the use of thecompound of formula (I) as described above as intermediate orcrosslinker or as monomer in polymerization reactions or inoligomerization reactions, in particular in dimerization reactions, inparticular, as monomer for the formation of poly(keto urethanes),poly(keto carbonates), poly(keto thiocarbonates, poly(keto ethers) orpolymers comprising a mixture of the functional groups selected from thegroup consisting of keto urethanes, keto carbonates, ketothiocarbonates, keto ethers, polyunsaturated urethanes andpolyunsaturated carbonates.

In one embodiment of the present invention, the inventive use of thecompound of formula (I) as described above is characterized in that n is2, 3, 4, 5 or 6, preferably 2, 3 or 4, more preferably 2 or 3, inparticular 2, and m is 0 as a monomer in polymerization reactions, inparticular, as monomer for the formation of poly(keto urethanes),poly(keto carbonates), poly(keto thiocarbonates), poly(keto ethers) orpolymers comprising mixture the functional groups consisting of ketourethanes, keto carbonates, keto thiocarbonates, keto ethers,polyunsaturated urethanes and polyunsaturated carbonates.

A further aspect of the present invention is the use of the compound offormula (I) as described above as reactive component in adhesive orsealing compositions, in compositions for coating materials, e.g. inlaminating processes, lacquers, paints, inks, building materials,elastomers, foams or for binding of fibers or particles or engineeringplastics.

The inventive compounds of formula (I) can be used together with apolyfunctional hardener as a second component in two component bondingagent systems, also called two pack adhesives, as described for examplein WO 2006/010408, WO 2016/2026652 A1, WO 2017/207461 A1, WO 2018054713A1 or WO 2018054609 A1. Alternatively, the inventive compounds offormula (I) can be used in one component bonding agent systems, alsocalled one pack adhesives, as described for example in WO 2008110394.

A further aspect of the present invention is a two-component compositioncomprising as a first component at least one compound of formula (I) asdescribed above, preferably wherein n in formula (I) is 2, 3, 4, 5 or 6,preferably 2, 3 or 4, more preferably 2 or 3, in particular 2, and m is0, and as a second component at least one multifunctional hardener thatcomprises at least two functional groups selected from the groupconsisting of primary amino groups, secondary amino groups, hydroxygroups, phosphine groups, phosphonate groups, carboxy- and mercaptangroups. Preferably, the functional groups of the hardener are selectedfrom aliphatic hydroxyl groups, aliphatic primary amino groups,aliphatic secondary amino groups, aliphatic phosphine groups, aliphaticphosphonate groups and aliphatic mercaptan groups, more preferablyselected from aliphatic hydroxyl groups, aliphatic primary amino groupsand aliphatic secondary amino groups and respective protected functionalgroups such as an imine, which liberates the amino group after areaction with water.

The inventive two-component compositions are also called two-packadhesives or two-pack binder compositions hereinafter.

The inventive two-component compositions (two-pack binder compositions)may also comprise one or more suitable catalysts for the hardening,which are guided in a known manner by the nature of the reactivefunctional groups of the multifunctional hardener. The two-pack adhesiveis preferably applied either in the form of a solution in an organicsolvent or solvent-free. “Solvent-free” means that less than 5% byweight, more preferably less than 2% by weight or zero organic solventor water is present.

Two-pack adhesives (also called two-pack binder compositionshereinafter) are understood to mean a binder comprising at least twopolyfunctional binder constituents which react with one another to formbonds and in doing so form a polymeric network. Due to thealkylidene-1,3-dioxolan-2-one groups present therein, the polymers ofthe invention can react with numerous nucleophilic groups to form bonds.Examples of such nucleophilic groups are particularly aliphatic hydroxylgroups, aliphatic primary and secondary amino groups, phosphine groups,especially aliphatic phosphine groups, phosphonate groups, especiallyaliphatic phosphonate groups, and analogous phosphorus compounds,carboxylate group and also mercaptan groups, especially aliphaticmercaptan groups.

Accordingly, two-pack binder compositions comprise, as well as at leastone compound of formula (I) of the invention, preferably additionally atleast one compound having at least 2 functional groups F, for example 2,3, 4, 5, 6, 7, 8, 9 or 10 functional groups F, which are selected fromaliphatic hydroxyl groups, aliphatic primary or secondary amino groups,aliphatic phosphine groups, aliphatic phosphonate groups, carboxylategroup and similar groups, and aliphatic mercaptan groups. Thesecompounds are also referred to hereinafter as hardeners. Preferredfunctional groups F are aliphatic hydroxyl groups and aliphatic primaryand secondary amino groups. Preferably, the amount of hardener isselected such that the molar ratio of functionalalkylidene-1,3-dioxolan-2-one groups of the formula Ito the functionalgroups F in the hardener is in the range from 1:10 to 10:1, particularlyin the range from 5:1 to 1:5 and especially in the range from 1:2 to2:1. The compound of formula (I) of the invention can be also mixed withknown cyclic exo vinyl carbonates, which react in the same manner as thecompounds of formula (I) or with other cyclic carbonates without a vinylfunction.

The hardener may be a low molecular weight substance, which means thatthe molecular weight thereof is below 500 g/mol, or an oligomeric orpolymeric substance having a number-average molecular weight above 500g/mol.

The hardeners preferred in accordance with the invention include aminichardeners, i.e. hardeners which have at least two primary or secondaryamino groups, and alcoholic hardeners, i.e. compounds which have atleast two hydroxyl groups.

The aminic hardeners, also amine hardeners hereinafter, include, forexample, aliphatic and cycloaliphatic polyamines, aromatic andaraliphatic polyamines and polymeric amines, for example amino resin,PEIor polylysine and polyamidoamines. Amine hardeners crosslink polymershaving 1,3-dioxolan-2-one groups, also called carbonate polymershereinafter, by reaction of the primary or secondary amino functions ofthe polyamines with the 1,3-dioxolan-2-one groups of the carbonatepolymers to form urethane functions. Preferred polyamine hardeners havean average of at least two primary or secondary amino groups permolecule, for example two, three or four primary or secondary aminogroups per molecule. They may also additionally comprise one or moretertiary amino groups. Suitable polyamines are, for example,

-   -   aliphatic polyamines such as ethylenediamine, 1,2- and        1,3-propanediamine, neopentanediamine, hexamethylenediamine,        octamethylenediamine, 1,10-diaminodecane, 1,12-diaminododecane,        diethylenetriamine, triethylenetetramine,        tetraethylenepentamine, 2,2-dimethylpropylenediamine,        trimethylhexamethylenediamine, 1-(3-aminopropyl)-3-aminopropane,        1,3-bis(3-aminopropyl)propane,        4-ethyl-4-methylamino-1-octylamine, and the like;    -   cycloaliphatic diamines, such as 1,2-diaminocyclohexane, 1,2-,        1,3-, 1,4-bis(amino-methyl)cyclohexane,        1-methyl-2,4-diaminocyclohexane,        N-cyclohexylpropylene-1,3-diamine,        4-(2-aminopropan-2-yl)-1-methylcyclohexane-1-amine,        isophoronediamine, 4,4′-diaminodicyclohexylmethane (Dicykan),        3,3′-dimethyl-4,4′-diaminodicyclohexylmethane,        3,3′,5,5′-tetramethyl-4,4′-diaminodicyclohexylmethane,        4,8-diaminotricyclo[5.2.1.0]decane, norbornanediamine,        menthanediamine, menthenediamine, and the like;    -   aromatic diamines, such as tolylenediamine, xylylenediamine,        especially meta-xylylenediamine (MXDA),        bis(4-aminophenyl)methane (MDA or methylenedianiline),        bis(4-aminophenyl) sulfone (also known as DADS, DDS or dapsone),        and the like;    -   cyclic polyamines, such as piperazine, N-aminoethylpiperazine,        and the like;    -   polyetheramines, especially difunctional and trifunctional        primary polyetheramines based on polypropylene glycol,        polyethylene glycol, polybutylene oxide, poly(l,4-butanediol),        polytetrahydrofuran (polyTHF) or polypentylene oxide, for        example 4,7,10-trioxatridecane-1,3-diamine,        4,7,10-trioxatridecane-1,13-diamine, 1,8-diamino-3,6-dioxaoctane        (XTJ-504 from Huntsman), 1,10-diamino-4,7-dioxadecane (XTJ-590        from Huntsman), 1,12-diamino-4,9-dioxadodecane (from BASF SE),        1,3-diamino-4,7,10-trioxatridecane (from BASF SE), primary        polyetheramines based on polypropylene glycol having a mean        molar mass of 230, for example polyetheramine D 230 (from BASF        SE) or Jeffamine® D 230 (from Huntsman), difunctional, primary        polyetheramines based on polypropylene glycol having a mean        molar mass of 400, e.g. polyetheramine D 400 (from BASF SE) or        Jeffamine® XTJ 582 (from Huntsman), difunctional, primary        polyetheramines based on polypropylene glycol having a mean        molar mass of 2000, for example polyetheramine D 2000 (from BASF        SE), Jeffamine® D2000 or Jeffamine® XTJ 578 (each from        Huntsman), difunctional, primary polyetheramines based on        propylene oxide having a mean molar mass of 4000, for example        polyetheramine D 4000 (from BASF SE), trifunctional, primary        polyetheramines prepared by reacting propylene oxide with        trimethylolpropane followed by an amination of the terminal OH        groups, having a mean molar mass of 403, for example        polyetheramine T 403 (from BASF SE) or Jeffamine® T 403 (from        Huntsman), trifunctional, primary polyetheramine prepared by        reacting propylene oxide with glycerol, followed by an amination        of the terminal OH groups, having a mean molar mass of 5000, for        example polyetheramine T 5000 (from BASF SE) or Jeffamine® T        5000 (from Huntsman), aliphatic polyetheramines formed from a        propylene oxide-grafted polyethylene glycol and having a mean        molar mass of 600, for example Jeffamine® ED-600 or Jeffamine®        XTJ 501 (each from Huntsman), aliphatic polyetheramines formed        from a propylene oxide-grafted polyethylene glycol and having a        mean molar mass of 900, for example Jeffamine® ED-900 (from        Huntsman), aliphatic polyetheramines formed from a propylene        oxide-grafted polyethylene glycol and having a mean molar mass        of 2000, for example Jeffamine® ED-2003 (from Huntsman),        difunctional, primary polyetheramine prepared by amination of a        propylene oxide-grafted diethylene glycol, having a mean molar        mass of 220, for example Jeffamine® HK-511 (from Huntsman),        aliphatic polyetheramines based on a copolymer of        poly(tetramethylene ether glycol) and polypropylene glycol        having a mean molar mass of 1000, for example Jeffamine® XTJ-542        (from Huntsman), aliphatic polyetheramines based on a copolymer        of poly(tetramethylene ether glycol) and polypropylene glycol        having a mean molar mass of 1900, for example Jeffamine® XTJ-548        (from Huntsman), aliphatic polyetheramines based on a copolymer        of poly(tetramethylene ether glycol) and polypropylene glycol        having a mean molar mass of 1400, for example Jeffamine® XTJ-559        (from Huntsman), polyethertriamines based on a butylene        oxide-grafted, at least trihydric alcohol having a mean molar        mass of 400, for example Jeffamine® XTJ-566 (from Huntsman),        aliphatic polyetheramines prepared by amination of butylene        oxide-grafted alcohols having a mean molar mass of 219, for        example Jeffamine® XTJ-568 (from Huntsman), polyetheramines        based on pentaerythritol and propylene oxide having a mean molar        mass of 600, for example Jeffamine® XTJ-616 (from Huntsman),        polyetheramines based on triethylene glycol having a mean molar        mass of 148, for example Jeffamine® EDR-148 (from Huntsman),        difunctional, primary polyetheramines prepared by amination of a        propylene oxide-grafted ethylene glycol, having a mean molar        mass of 176, for example Jeffamine® EDR-176 (from Huntsman), and        also polyetheramines prepared by amination of        polytetrahydrofuran (polyTHF) having a mean molar mass of 250,        for example PolyTHF-amine 350 (BASF SE), and mixtures of these        amines;    -   polyamidoamines (amidopolyamines), which are obtainable by        reaction of dimeric fatty acids (for example dimeric linoleic        acid) with polyamines of low molecular weight, such as        diethylenetriamine, 1-(3-aminopropyl)-3-aminopropane or        triethylenetetramine, or other diamines, such as the        aforementioned aliphatic or cycloaliphatic diamines;    -   adducts obtainable by reaction of amines, especially diamines,        with a deficiency of epoxy resin, preference being given to        using those adducts in which about 5% to 20% of the epoxy groups        have been reacted with amines, especially diamines;    -   phenalkamines as known from epoxide chemistry;    -   Mannich bases which are prepared, for example, by condensation        of polyamines, preferably diethylenetriamine,        triethylenetetramine, isophoronediamine, 2,2,4- or        2,4,4-trimethylhexamethylenediamine, 1,3- and        1,4-bis(aminomethyl)cyclohexane, with aldehydes, preferably        formaldehyde, and mono- or polyhydric phenols having at least        one aldehyde-reactive core site, for example the various cresols        and xylenols, p-tert-butylphenol, resorcinol,        4,4′-dihydroxydiphenylmethane,        4,4′-dihydroxydiphenyl-2,2-propane, but preferably phenol;        and mixtures of the aforementioned amine hardeners, especially        mixtures of difunctional amines from the group of the aliphatic,        cycloaliphatic and aromatic amines with the aforementioned        polyetheramines.

Preferred aminic hardeners are aliphatic polyamines, especially2,2-dimethylpropylenediamine, aromatic diamines, especiallym-xylylenediamine (MXDA) and cycloaliphatic diamines, especiallyisophoronediamine, N-cyclohexylpropylene-1,3-diamine, Methylcyclohexanediamine and 4,4′-diaminodicyclohexylmethane (Dicykan).Preference is also given to difunctional or trifunctional primarypolyetheramines based on polypropylene glycol , for example Jeffamine® D230 or Jeffamine® T 403. Particular preference is given to polyamines inwhich there is high mobility and low steric hindrance around the aminogroup, for example 4,9-dioxadodecane-1,12-diamine,4,7,10-trioxatridecane-1,13-diamine, PolyTHF Amine 350 (BASF SE).

Preference is also given to mixtures of the amines specified aspreferred, for example mixtures comprising2,2-dimethyl-1,3-propanediamine and isophoronamine.

The compositions of the present invention may be used as a one componentmixture with at least one latent hardener which is activatable bymoisture, said hardener being selected from the group consisting ofoxazolidines, aldimines, ketimines and enamines.

The alcoholic hardeners include particularly aliphatic andcycloaliphatic alcohols of low molecular weight and higher molecularweight. Alcoholic hardeners crosslink carbonate polymers by reaction ofthe primary or secondary alcohol functions with the 1,3-dioxolan-2-onegroups of the carbonate polymers to form diesters of carbonic acid.Preferred alcoholic hardeners have an average of at least two primary orsecondary hydroxyl groups per molecule, for example two, three or fourprimary or secondary hydroxyl groups per molecule. Suitable alcoholichardeners of low molecular weight are, for example, butane-1,4-diol,ethylene glycol, diethylene glycol, triethylene glycol, neopentylglycol, propane-1,3-diol, pentane-1,5-diol, hexane-1,6-diol, glycerol,diglycerol, pentaerythritol, dipentaerythritol, isosorbide, sugaralcohols such as sorbitol and mannitol.

Suitable alcoholic hardeners are also higher molecular weight polymericpolyols, for example polyester polyols, polycarbonate polyols, polyetherpolyols, polyacrylate polyols and polyvinyl alcohols. Suitable polymericpolyol hardeners preferably have a mean OH functionality of at least 1.5mol and especially at least 1.8, for example in the range from 1.5 to 10and especially in the range from 1.8 to 4. The mean OH functionality isunderstood to mean the mean number of OH groups per polymer chain.Typical polymeric polyol components preferably have a number-averagemolecular weight of about 250 to 50 000 g/mol, preferably of about 500to 10 000 g/mol. Preferably, at least 50 mol % of the hydroxyl groupspresent in the polymeric polyol component are primary hydroxyl groups.

Preferably, polyester polyols are linear or branched polymeric compoundshaving ester groups in the polymer backbone and having free hydroxylgroups at the ends of the polymer chain. Preferably, these arepolyesters which are obtained by polycondensation of dihydric alcoholswith dibasic carboxylic acids, optionally in the presence of higherpolyhydric alcohols (e.g. tri-, tetra-, penta- or hexahydric alcohols)and/or higher polybasic polycarboxylic acids. Rather than the free di-or polycarboxylic acids, it is also possible to use the correspondingdi- or polycarboxylic anhydrides or corresponding di- or polycarboxylicesters of lower alcohols or mixtures thereof for preparation of thepolyester polyols. The di- or polycarboxylic acids may be aliphatic,cycloaliphatic, araliphatic, aromatic or heterocyclic, preferably have 2to 50 and especially 4 to 20 carbon atoms and may optionally besubstituted, for example by halogen atoms, and/or be unsaturated.Examples thereof include: suberic acid, azelaic acid, phthalic acid,isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride,hexahydrophthalic anhydride, tetrachlorophthalic anhydride,endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleicacid, maleic anhydride, alkenylsuccinic acid, fumaric acid and dimericfatty acids. Useful diols for the preparation of the polyester polyolsinclude especially aliphatic and cycloaliphatic diols having preferably2 to 40 and especially 2 to 20 carbon atoms, for example ethyleneglycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol,butane-1,4-diol, butene-1,4-diol, butyne-1,4-diol, pentane-1,5-diol,neopentyl glycol, bis(hydroxymethyl)cyclohexanes such as1,4-bis(hydroxymethyl)cyclohexane, 2-methylpropane-1,3-diol,methylpentanediols, and also diethylene glycol, triethylene glycol,tetraethylene glycol, polyethylene glycol, dipropylene glycol,polypropylene glycol, dibutylene glycol and polybutylene glycols.Preference is given to alcohols of the general formula HO—(CH₂)_(x)—OH,where x is a number from 2 to 20, preferably an even number from 2 to12. Examples thereof are ethylene glycol, butane-1,4-diol,hexane-1,6-diol, octane-1,8-diol and dodecane-1,12-diol. Additionallypreferred are neopentyl glycol and pentane-1,5-diol.

Suitable alcoholic hardeners are also lactone-based polyester polyols,these being homo- or copolymers of lactones, preferably terminalhydroxyl-containing addition products of lactones onto suitabledifunctional starter molecules. Useful lactones are preferably thosewhich derive from compounds of the general formula HO—(CH₂)_(z)—COOHwhere z is a number from 1 to 20 and one hydrogen atom of one methyleneunit may also be substituted by a C₁-C₄-alkyl radical. Examples areε-caprolactone, β-propiolactone, γ-butyrolactone and/ormethyl-ε-caprolactone and mixtures thereof. Suitable starter moleculesare, for example, the low molecular weight dihydric alcohols mentionedabove as a formation component for the polyester polyols. Thecorresponding polymers of ε-caprolactone are particularly preferred. Itis also possible to use lower polyester diols or polyether diols asstarters for preparation of the lactone polymers. Rather than thepolymers of lactones, it is also possible to use the correspondingchemically equivalent polycondensates of the hydroxycarboxylic acidscorresponding to the lactones.

Examples of suitable polyester polyols are, for example, the polyesterpolyols known from Ullmanns Enzyklopädie der Technischen Chemie, 4thEdition, Volume 19, pages 62 to 65.

In addition, polycarbonate polyols are also useful, as obtainable, forexample, by reaction of phosgene with an excess of the low molecularweight alcohols mentioned as formation components for the polyesterpolyols.

The polyether polyols are especially polyether polyols preparable bypolymerization of ethylene oxide, propylene oxide, butylene oxide,tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, forexample in the presence of BF₃ or by addition of these compounds,optionally in a mixture or in succession, onto bi- or polyfunctionalstarter components having reactive hydrogen atoms, such as polyols orpolyfunctional amines, for example water, ethylene glycol,propane-1,2-diol, propane-1,3-diol, 1,1-bis(4-hydroxyphenyl)propane,trimethylolpropane, glycerol, sorbitol, ethanolamine or ethylenediamine.Also useful are sucrose polyethers (see DE 1176358 and DE 1064938), andformitol- or formose-started polyethers (see DE 2639083 and DE 2737951).

Likewise suitable are polyhydroxy olefins, preferably those having 2terminal hydroxyl groups, e.g. α,ω-dihydroxypolybutadiene.

Likewise suitable are polyhydroxypolyacrylates, where the hydroxylgroups may be arranged laterally or terminally. Examples thereof areα,ω-dihydroxypoly(meth)acrylic esters obtainable by homo- orcopolymerization of alkyl esters of acrylic acid and/or of methacrylicacid in the presence of regulators comprising OH groups, such asmercaptoethanol or mercaptopropanol, and subsequent transesterificationwith a low molecular weight polyol, for example an alkylene glycol suchas butanediol. Such polymers are known, for example, from EP-A 622 378.Examples thereof are additionally polymers obtainable bycopolymerization of alkyl esters of acrylic acid and/or of methacrylicacid with hydroxyalkyl esters of ethylenically unsaturated carboxylicacid such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutylacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate orhydroxybutyl methacrylate.

Also suitable are polyvinyl alcohols, which can preferably be obtainedby full or partial hydrolysis of polyvinyl esters, especially polyvinylacetate. If the polyvinyl esters, preferably polyvinyl acetate, are inpartly hydrolyzed form, preferably not more than 50% to 95% of the estergroups are in hydrolyzed form as hydroxyl groups. If the polyvinylesters, preferably polyvinyl acetate, are in fully hydrolyzed form,generally more than 95% up to 100% of the ester groups are in hydrolyzedform as hydroxyl groups.

Alcoholic hardeners preferred among the higher molecular weightpolymeric polyols are especially polyacrylate polyols, these beingobtainable, for example, under the Joncryl® brand name from BASF SE,e.g. Joncryl® 945.

Suitable hardeners are also amino acids, for example lysine, arginine,glutamine and asparagine, and the stereoisomers thereof and mixturesthereof.

It will be appreciated that it is also possible to use mixtures ofdifferent hardeners, for example mixtures of one or more aminichardeners with one or more alcoholic hardeners, mixtures of one or moreaminic hardeners with one or more amino acids, or mixtures of one ormore alcoholic hardeners with one or more amino acids.

In the binder compositions of the invention, the total amount ofhardeners is preferably 0.1% by weight to 50% by weight, frequently 0.5%to 40% by weight and especially 1% to 30% by weight, based on the totalamount of carbonate polymers plus hardeners used.

The binder composition can be hardened thermally by heating the mixtureof polymer of the invention and hardener to a temperature above themixing temperature. The hardening can also be effected at lowertemperatures. Typically, the binder compositions of the invention arehardened at temperatures in the range from 0 to 200° C., preferably inthe range from 5 to 180° C. and especially in the range from 10 to 150°C. The temperature which is suitable depends on the respective hardenersand the desired hardening rate, and can be determined in the individualcase by the person skilled in the art, for example by simple preliminarytests. In the lower temperature range (5 to approx. 35° C.), which ofcourse corresponds to the usually prevailing ambient temperature, it isof course sufficient to mix polymer of the invention and hardener.Alternatively, the hardening is preferably microwave-induced.

The two-pack binder compositions may also comprise one or more suitablecatalysts for the hardening, which are guided in a known manner by thenature of the reactive functional groups F. The catalysts are, ifdesired, used in proportions of 0.01% by weight to about 10% by weight,based on the total weight of the polymers of the invention havingfunctional alkylidene-1,3-dioxolan-2-one groups of the formula I and ofthe hardener. In one configuration, no catalysts are required,particularly in the case of hardeners which have amino groups asfunctional groups, which means that the content of catalysts in thecomposition in that case is less than 0.01% by weight. Catalysts areused with preference when the hardener has reactive groups F other thanamino groups, especially when the hardener has hydroxyl groups.

Catalysts used with preference are basic catalysts, more preferablyorganic amines and organic phosphines. Among the organic amines,preference is given to amidine bases, for example1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and1,5-diazabicyclo[4.3.0]non-5-ene (DBN), and to mono-C₁-C₆-alkyl-,di-C₁-C₆-alkyl- and tri-C₁-C₆-alkylamines, especially triethylamine andtert-butylamine. Among the organic phosphines, preference is given totrialkylphosphines and tri-arylphosphines, for exampletri-n-butylphosphine and triphenylphosphine. The catalysts can of coursealso be used as mixtures, optionally in combination withtri-C₁-C₆-alkylammonium halides and copper salts, for exampletriphenylphosphine in combination with a tri-C₁-C₆-alkyl-ammonium halideand a copper salt, e.g. copper(I) chloride, copper(I) bromide,copper(II) chloride or copper(II) sulfate. Guanidine, phenolate,benzoate

As well as the aforementioned constituents, the two-pack bindercomposition may comprise the additives customary therefor. The choice ofsuitable conventional additives for the composition of the inventiondepends on the particular end use of the two-pack binder composition andcan be determined in the individual case by the person skilled in theart.

Suitable additives comprise, for example, antioxidants, UVabsorbers/light stabilizers, metal deactivators, antistats, reinforcers,fillers, antifogging agents, blowing agents, biocides, plasticizers,lubricants, emulsifiers, colorants, pigments, rheology agents, impacttougheners, adhesion regulators, optical brighteners, flame retardants,antidripping agents, nucleating agents, wetting agents, thickeners,protective colloids, defoamers, tackifiers, solvents and reactivediluents, and mixtures thereof.

Fillers may be organic and inorganic in nature; preferred inorganicfillers take the form of platelets which can be aligned to form layershaving enhanced barrier action against liquids and gases. Examples aresheet silicates such as montmorillonite and hectorite, as described, forexample, in WO 2011/089089, WO 2012/175427 or in WO 2012/175431.Preference is given to sheet silicates having an aspect ratio of atleast 50, at least 400, or at least 1000, and especially greater than orequal to 10 000. The layer thickness is, for example, about 1 nm. Thesheet silicates may be of natural or synthetic origin. Suitable sheetsilicates are, for example, montmorillonite, bentonite, kaolinite, mica,hectorite, fluorohectorite, saponite, beidellite, nontronite,stevensite, vermiculite, fluorovermiculite, halloysite, volkonskoite,suconite, magadite, sauconite, stibensite, stipulgite, attapulgite,illite, kenyaite, smectite, allevardite, muscovite, palygorskite,sepiolite, silinaite, grumantite, revdite, zeolite, fuller's earth,natural or synthetic talc or mica, or permutite. Particular preferenceis given to montmorillonite (aluminum magnesium silicate), hectorite(magnesium lithium silicate), synthetic fluorohectorite and exfoliated,organically modified smectites. The sheet silicates may be modified orunmodified. Preference is given to cationically modified sheetsilicates. “Cationically modified” means that inorganic cations in thesheet silicate have been at least partly exchanged for organic cations,for example by an ion exchange method. Organic cations are organiccompounds having at least one cationic group, for example quaternaryammonium group, phosphonium group, pyridinium group or the like, or acationic amine salt.

Any light stabilizers/UV absorbers, antioxidants and metal deactivatorsused preferably have a high migration stability and thermal stability.They are selected, for example, from groups a) to t). The compounds ofgroups a) to g) and i) are light stabilizers/UV absorbers, whilecompounds j) to t) act as stabilizers.

-   a) 4,4-diarylbutadienes,-   b) cinnamic esters,-   c) benzotriazoles,-   d) hydroxybenzophenones,-   e) diphenyl cyanoacrylates,-   f) oxamides,-   g) 2-phenyl-1,3,5-triazines,-   h) antioxidants,-   i) nickel compounds,-   j) sterically hindered amines,-   k) metal deactivators,-   l) phosphites and phosphonites,-   m) hydroxylamines,-   n) nitrones,-   o) amine oxides,-   p) benzofuranones and indolinones,-   q) thio synergists,-   r) peroxide-destroying compounds,-   s) polyamide stabilizers and-   t) basic costabilizers.

The two-pack adhesive is preferably free of isocyanates, meaning that itis preferably does not comprise any isocyanate compounds as hardeners.The two-pack adhesive is preferably either in the form of a solution inan organic solvent or is solvent-free. “Solvent-free” means that lessthan 5% by weight, more preferably less than 2% by weight or zeroorganic solvent or water is present.

The inventive two-component composition usually develops high bindingstrength in a short time, in particular with amine hardeners, already atroom temperature.

The inventive two-component composition can be applied as adhesive inlaminating processes such as described in detail in WO 2017/207461 A1,on pages 20 to 25.

The inventive two-component composition can also be applied for bondingof solid substrates as wood, metals various plastics, composites, paper,cardboard, fiber reinforced materials, concrete or various mineralbuilding materials.

The inventive compounds of formula (I) can be used in combination withpolyfunctional amines or polyols as a component of coating materialcompositions for the coating of metallic or non-metallic surfaces suchas described in WO 2015/039807.

The inventive compounds of formula (I) together with an appropriatehardener as described above forms polymers, which fulfil the intendedapplication. Alternatively, the inventive compounds of formula (I),wherein m is 1 or 2 can be also polymerized alone or together withsuitable further monomers comprising at least one polymerizablecarbon-carbon double bonds to form polymers, that means homo- orcopolymers.

Therefore, a further aspect of the present invention is a polymer formedfrom one or more monomers, wherein at least one monomer is a compound offormula (I) as described above.

In one embodiment of the present invention, the inventive polymer ischaracterized in that the polymer is a reaction product of the compoundof formula (I) as described above and one or more compounds whichcomprise at least two functional groups selected from the groupconsisting of primary amino groups, secondary amino groups, hydroxygroups, carboxylate groups, phosphine groups, phosphonate groups andmercaptan groups, preferably selected from polyols, polyacids,polyamines, polyamido-amines and mixtures thereof.

A further aspect of the present invention is a two-component compositioncomprising as a first component a polymer as described above and as asecond component at least one multifunctional hardener that comprises atleast two functional groups selected from the group consisting ofprimary amino groups, secondary amino groups, hydroxy groups, phosphinegroups, phosphonate groups and mercaptan groups.

A further aspect of the present invention is the use of the compound offormula (I), of the two-component composition as described above or ofthe polymer as described above as a component of an adhesive and/orsealant for rigid and flexible parts, made from metal, plastic, paper,paperboard, textiles, glass, leather, wood and inorganic materials.

A further aspect of the present invention is the use of the compound offormula (I), of the two-component composition as described above or ofthe polymer as described above as a component of a coating for rigid andflexible substrates, made from metal, plastic, paper, paperboard,textiles, glass, leather, wood and inorganic materials.

A further aspect of the present invention is the use of the compound offormula (I), of the two-component composition as described above or ofthe polymer as described above as a component of a binder for fibers,particles and pigments.

A further aspect of the present invention is the use of the compound offormula (I), of the two-component composition as described above or ofthe polymer as described above as a component of foam rubbers,preferably together with an appropriate foaming agent.

A further aspect of the present invention is the use of any compound asdescribed above, that means the compound of formula (I), the polymersobtainable by polymerizing the compound of formula (I) alone or togetherwith additional monomers and the above described two-componentcompositions, as an intermediate for the preparation of polyunsaturatedcompounds by reacting a (oligo/poly)-functional nucleophile with acompound of formula (I). The obtained reaction product can besubsequently applied to further curing (e.g. radical induced curing).

The invention is illustrated by the examples which follow, but these donot restrict the invention.

Figures in percent are each based on % by weight, unless explicitlystated otherwise.

General

All chemicals and solvents were purchased from Sigma-Aldrich or ABCR andused without further purification.

¹H and ¹³C NMR spectra were recorded on Bruker Avance 200 MHz and 400MHz spectrometer and were referenced to the residual proton (¹H) orcarbon (¹³C) resonance peaks of the solvent.

Chemical shifts (δ) are reported in ppm.

Used abbreviations: Davephos-LigandA=2-Dicyclohexylphosphino-2′-(N,N-dimethylamino)biphenyl;DCM=Dichloromethane; DIPEA=N,N-Diisopropylethylamine;DMAP=4-Dimethylaminopyridine; DMF=Dimethylformamide; PE=Petroleum ether;THF=Tetrahydrofuran; TMEDA=Tetramethylethylenediamine;

I. Synthesis of the Starting Materials and of Compounds of Formula (II)

I.1 4-hydroxybut-2-yn-1-yl methacrylate

Distilled Et₃N (5.6 mL, 40.6 mmol, 1.4 eq.) was added to a solution ofbut-2-yne-1,4-diol (2.5 g, 29.0 mmol, 1.0 eq.) in dry DCM/THF (12 mL/4mL), and the resulting suspension was stirred at room temperature untildissolution was complete. Methacrylic anhydride (4.75 mL, 31.9 mmol, 1.1eq.) was then added to the reaction mixture at 0° C. dropwise over 30min. The reaction mixture was then warmed to room temperature andstirred overnight. Water was added and the reaction mixture wasextracted with DCM (3022×2 mL). The collected organic layers were driedand the solvents were evaporated in vacuo. Flash chromatography of thecrude products (silica gel, EtOAc/PE 2:3) gave the pure product as acolourless oil (2.3 g, 52%).

¹H NMR (400 MHz, CDCl₃): δ=6.12-6.13 (m, 1H), 5.60-5.58 (s, 1H),4.76-4.75 (m, 2H), 4.28-4.27 (m, 2H), 2.61 (br.s, 1H), 1.93-1.92 (m,3H). ¹³C NMR (101 MHz, CDCl₃): δ=166.9, 135.7, 126.7, 85.2, 79.7, 52.6,50.9, 18.3. HRMS (ESI, 70 eV): m/z calcd. for C₈H₁₀O₃: 154.0625 [M+];found: 154.0618.

I.2 2-((((4-hydroxybut-2-yn-1-yl)oxy)carbonyl)amino)ethyl methacrylate

Distilled Et₃N (8.9 mL, 63.8 mmol, 1.1 eq.) was added to a solution ofbut-2-yne-1,4-diol (5.0 g, 58.0 mmol, 1.0 eq.) in dry DCM/THF (24 mL/8mL), and the resulting suspension was stirred at room temperature untildissolution was complete. 2-isocyanatoethyl methacrylate (8.6 mL, 58.0mmol, 1.0 eq.) was then added to the reaction mixture at 0° C. dropwiseover 30 min. The reaction mixture was then warmed to room temperatureand stirred overnight. Water was added and the reaction mixture wasextracted with DCM (3044×4 mL). The collected organic layers were driedand the solvents were evaporated in vacuo. Flash chromatography of thecrude (silica gel, EtOAc/PE 7:3) gave the pure product (R_(f)=0.35) as acolourless oil (8.4 g, 60%)

¹H NMR (400 MHz, CDCl₃): δ=6.13-6.12 (m, 1H), 5.61-5.60 (s, 1H), 5.06(br.s, 1H), 4.73 (s, 2 H), 4.31-4.30 (m, 2H), 4.26-4.23 (m, 2H),3.54-3.50 (m, 2H), 1.95 (s, 3H), 1.73 (br.s, 1H). ¹³C NMR (101 MHz,CDCl₃): δ=167.2, 155.5, 135.9, 126.1, 84.9, 80.2, 63.6, 52.9, 51.1,40.4, 18.3.

I.3 4,4′-((1,4-phenylenebis(methylene))bis(oxy))bis(but-2-yn-1-ol)

But-2-yne-1,4-diol (2.6 g, 30.2 mmol, 4.0 eq.) dissolved in anhydrousTHF (10 mL) was added dropwise into a 100 mL three-neck round bottomflask containing a solution of NaH (0.37 g, 15.2 mmol, 2.0 eq.) inanhydrous THF (12 mL). After stirring for 30 min, 1,4-bis(bromomethyl)benzene (2.0 g, 7.58 mmol, 1.0 eq.) was added and the mixture wasrefluxed overnight. The solvent was removed in vacuo and the residue waspurified by column chromatography (silica gel, EtOAc/PE 7:3) to affordthe desired product as white solid (1.62 g, 78%).

¹H NMR (400 MHz, CDCl₃): δ=7.35-7.27 (m, 4H), 4.60 (s, 4H), 4.33 (br.s,4H), 4.22-4.20 (m, 4H), 1.99 (br.s, 2H). ¹³C NMR (101 MHz, CDCl₃):δ=137.2 (2C), 128.4 (4C), 84.9 (2C), 81.9 (2C), 71.6 (2C), 57.6 (2C),51.3 (2C). IR (KBr): 3279, 3201, 2914, 1402, 1368, 1342, 1236, 1138,1069, 1007, 989, 839, 759, 585, 537. HRMS (EI): m/z calcd. for C₁₆H₁₈O₄:274.1176 [M⁺]; found: 274.1199.

I.4 bis(4-hydroxybut-2-yn-1-yl)(4-methyl-1,3-phenylene)dicarbamate

2,4-diisocyanato-1-methylbenzene (1.0 g, 5.8 mmol, 1.0 eq.) dissolved inanhydrous DMF (5.0 mL) was added dropwise (2 drop/sec) into an argonpurged 100 mL three-neck round bottom flask containingbut-2-yne-1,4-diol (1.5 g, 17.4 mmol, 3.0 eq.) at 120° C. After theaddition was complete, the reaction mixture was further stirred for 1 hat 120° C. after which it was brought down to room temperature.Distilled water (90 mL) was then added to the above reaction mixture andthe product was let to crystallize in the freezer overnight. Thecrystals were filtered and recollected in a 250 mL round bottom flaskcontaining 150 mL water. The mixture was then refluxed at 110° C.,followed by hot filtration. The oligomers were separated by filtrationwhile the filtrate at the bottom was cooled down to obtain the productas a white solid (1.2 g, 60%).

¹H NMR (400 MHz, CD₃CN): δ=7.79 (br.s,1H), 7.73 (br.s, 1H), 7.21 (s,1H), 7.18-7.15 (m, 1H), 7.13-7.11 (m, 1H), 4.78-4.75 (m, 4H), 4.21-4.18(m, 4H), 3.18-3.14 (m, 2H), 2.18 (s, 3H). ¹³C NMR (101 MHz, CD₃CN):δ=154.4, 153.9, 137.8, 137.2, 131.6, 126.0, 116.2, 114.4, 86.5 (2C),80.0 (2C), 53.6 (2C), 53.4, 50.6, 17.3. IR (KBr): 3292, 1704, 1605,1539, 1498, 1451, 1429, 1318, 1283, 1235, 1185, 1144, 1060, 1015, 882,817, 762. HRMS (ESI): m/z calcd. for C₁₇H₁₈N₂O₆: 369.106 [M+Na⁺] found:369.106.

I.5 1,8-Bis(4-hydroxy-2-butyn-1-oxy)-3,6-dioxaoctane

The diol was synthesized in two steps.

I.5.a Synthesis of 4,7,10,13-tetraoxahexadeca-1,15-diyne

In an argon flushed 100 mL three-neck round bottom flask was charged asolution of 2,2′-(ethane-1,2-diylbis(oxy))bis(ethan-1-ol) (2.13 g, 14.2mmol, 1 eq.) in THF (5.0 mL) to a cooled (0° C.) suspension of t-BuOK(3.77 g, 32.0 mmol, 2.3 eq.) in 30 mL of THF. The resulting reactionmixture was allowed to warm to room temperature and was then addeddropwise to an ice cooled solution (0° C.) of propargyl bromide (6.3 mL,56.5 mmol, 4.0 eq.) in 120 mL of THF, under argon atmosphere. Thereaction mixture was stirred for an additional 18 h and the reaction letto warm to room temperature. A 3:1 brine/water (75 mL) solution was thenadded to the above mixture and the aqueous layer was extracted withEtOAc (35050×50 mL) followed by drying in vacuo. The residue waspurified by flash chromatography on silica gel (EtOAc/PE 1:1) to affordbis(propargyl ether) (2.24 g, 70%) as yellow oil.

I.5.b Synthesis of 1,8-Bis(4-hydroxy-2-butyn-1-oxy)-3,6-dioxaoctane

In an argon-flushed 250 mL three-neck round bottom flask was added asolution of bis(propargyl) ether (2.5 g, 10.9 mmol, 1 eq.) in 91 mL ofTHF and TMEDA (16.7 mL, 11.8 mmol, 10 eq.). The mixture was then cooledto −78° C., followed by the drop-wise addition of n-BuLi (16.0 mL, 1.6 Msolution, 26.6 mmol, 2.4 eq.). After an additional 5 min stirring, asuspension of paraformaldehyde (7.2 g, 22 mmol) in 7 mL of THF underargon was added via syringe. The reaction mixture was slowly allowed towarm to room temperature and stirred for an additional 1 h beforediluting with 150 mL of saturated aqueous NaH₂PO₄. The aqueous layer wasextracted with EtOAc (6033×3 mL), and the combined organic layers werewashed with120 mL of saturated NaHCO₃ and 120 mL of brine. The residueupon drying and concentration was purified by flash chromatography(EtOAc/MeOH 98:2) to afford the diol (R_(f) 0.35) as a pale yellow solid(1.3 g, 42%).

¹H NMR (400 MHz, CDCl₃): δ=4.25-4.24 (m, 4H), 4.20-4.19 (m, 4H),3.67-3.63 (m, 12H), 3.05 (br.s, 2H). ¹³C NMR (101 MHz, CDCI₃): δ=85.2(2C), 81.3 (2C), 70.6 (2C), 70.5 (2C), 69.1 (2C), 58.7 (2C), 50.7 (2C).HRMS (ESI, 70 eV): m/z calcd. for C₁₄H₂₂O₆: 309.131 [M+Na⁺]; found:309.131.

II. Synthesis of the Starting Materials and of Compounds of Formula (I)General Reaction Procedure

A steel autoclave was charged with Alkynol, in particular compounds ofgeneral formula (II) (5.0 mmol), AgOAc (1 or 2 mol %), andDavephos-Ligand A (1 or 2 mol %) and MeCN (10 mL). The reaction mixturewas pressurized with CO₂ (20 bar) and stirred at room temperature for 18h. Then CO₂ overpressure was carefully released and solvent evaporated.The resulting crude mixture was purified by flash column chromatography(silica gel, EtOAc/PE gradient).

Isolated Products

II.1 (Z)-4-(2-hydroxyethylidene)-1,3-dioxolan-2-one

Colorless oil, yield: 0.45 g (65%). ¹H NMR (200 MHz, CDCl₃): δ=4.97-4.88(m, 3H), 4.18-4.15 (m, 2H), 3.33 (s, 1H). ¹³C NMR (50 MHz, CDCl₃):δ=152.9, 143.2, 102.4, 67.6, 55.7. HRMS (EI): m/z calcd. for C₅H₆O₄:130.0260 [M⁺]; found: 130.0259.

II.2 (Z)-2-(2-oxo-1,3-dioxolan-4-ylidene)ethyl methacrylate

White solid, yield: 0.81 g (82%). mp: 36.1-36.3° C. ¹H NMR (400 MHz,CDCl₃) δ=6.12-6.11 (m, 1H), 5.59-5.58 (m, 1H), 5.02-4.99 (m, 3H),4.80-4.78 (m, 2H), 1.94 (s, 3H). ¹³C NMR (101 MHz, CDCl₃) δ=167.2,152.1, 145.4, 136.1, 126.2, 98.1, 67.4, 58.0, 18.4. IR (KBr): 3402,2933, 2356, 216.9, 1818, 1707, 1723, 1632, 1534, 1455, 1400, 1383, 1326,1288, 1229, 1156, 1133, 1088, 1045, 1011, 971, 920, 868, 841, 817, 766,732, 645, 617, 571. HRMS (EI): m/z calcd. for C₉H₁₀O₅: 198.0523 [M⁺];found: 198.0519. Anal. Calcd. for C₉H₁₀O₅: C 54.55%, H 5.09%, Found: C54.77%, H 5.13%.

II.3(Z)-2-(((2-(2-oxo-1,3-dioxolan-4-ylidene)ethoxy)carbonyl)amino)ethylmethacrylate

White solid, yield: 1.34 g (94%). mp: 86.5-86.7° C. ¹H NMR (400 MHz,CDCl₃) δ=6.12-6.11 (m, 1H), 5.59-5.57 (m, 1H), 5.00-4.97 (m, 3H),4.71-4.69 (m, 2H), 4.24-4.21 (m, 2H), 3.51-3.47 (m, 2H), 1.94 (s, 3H).¹³C NMR (101 MHz, CDCl₃) δ=167.4, 156.2, 152.1, 145.2, 136.1, 126.2,98.6, 67.4, 63.7, 58.3, 40.4, 18.4. IR (KBr): 3360, 3060, 1826, 1726,1690, 1632, 1539, 1471, 1437, 1385, 1327, 1306, 1253, 1217, 1139, 1046,1012, 967, 936, 873, 805, 760, 736, 621, 557. HRMS (ESI): m/z calcd. forC₁₂H₁₅NO₇: 308.074 [M+Na⁺]; found: 308.074. Anal. Calcd. for C₁₂H₁₅NO₇:C 50.53%, H 5.30%, N 4.91%, Found: C 50.24%, H 5.06%, N 5.06%.

II.4(4Z,4′Z)-4,4′-(((1,4-phenylenebis(methylene))bis(oxy))bis(ethan-2-yl-1-ylidene))bis(1,3-dioxolan-2-one)

White solid, yield: 1.56 g (86%). mp: 108.6-109.0° C. ¹H NMR (400 MHz,CDCl₃) δ=7.33-7.26 (m, 4H), 5.00-4.93 (m, 6H), 4.52 (m, 4H), 4.21-4.16(m, 4H). ¹³C NMR (101 MHz, CDCl₃) δ=152.2 (2C), 144.0 (2C), 137.4 (2C),128.0 (4C), 100.3 (2C), 72.5 (2C), 67.3 (2C), 63.3 (2C). IR (KBr): 2855,1833, 1702, 1461, 1385, 1295, 1212, 1134, 1085, 1055, 1035, 976, 905,835, 821, 763. HRMS (ESI): m/z calcd. for C₁₈H₁₈O₈: 363.107 [M+H⁺];found: 363.107. Anal. Calcd. for C₁₈H₁₈O₈: C 59.67%, H 5.01%, Found: C59.54%, H 4.76%.

II.5bis((Z)-2-(2-oxo-1,3-dioxolan-4-ylidene)ethyl)(4-methyl-1,3-phenylene)dicarbamate

White solid, yield: 2.02 g (93%). mp: 175.5-176.1° C. ¹H NMR (400 MHz,CD₃CN) δ=7.75-7.70 (m, 2H), 7.12-7.11 (m, 3H), 5.05-5.00 (m, 6H),4.76-4.69 (m, 4H), 2.15 (s, 3H). ¹³C NMR (101 MHz, CD₃CN) δ=154.9,154.4, 153.7, 147.3 (2C), 138.1, 137.4, 131.6 (2C), 125.7, 116.1, 114.4,98.2 (2C), 68.9 (2C), 59.2, 59.0, 17.3. IR (KBr): 3360, 1830, 1723,1606, 1542, 1457, 1387, 1284, 1224, 1179, 1130, 1098, 1042, 874, 815,764, 730, 566. HRMS (ESI): m/z calcd. for C₁₉H₁₈N₂O₁₀: 457.086 [M+Na⁺];found: 457.085. Anal. Calcd. for C₁₉H₁₈N₂O₁₀: C 52.54%, H 4.18%, N6.45%, Found: C 52.62%, H 4.22%, N 6.55%.

II.6(4Z,4′Z)-4,4′-(3,6,9,12-tetraoxatetradecane-1,14-diylidene)bis(1,3-dioxolan-2-one)

Colorless oil, yield: 1.78 g (95%). ¹H NMR (400 MHz, CDCl₃) δ=5.00-4.90(m, 6H), 4.20-4.15 (m, 4H), 3.65-3.58 (m, 12H). ¹³C NMR (101 MHz, CDCl₃)δ=152.4 (2C), 144.1 (2C), 100.4 (2C), 70.8 (2C), 70.7 (2C), 69.9 (2C),67.5 (2C), 64.3 (2C). IR (KBr): 2872, 1833, 1723, 1464, 1381, 1297,1214, 1131, 1106, 1046, 949, 870, 765, 733. HRMS (ESI): m/z calcd. forC₁₆H₂₂O₁₀: 397.110 [M+Na⁺]; found: 397.110. Anal. Calcd. for C₁₆H₂₂O₁₀:C 51.34%, H 5.92%, Found: C 51.48%, H 6.00%.

III. 5,9,14,18-tetraoxadocosa-2,20-diyne-1,7,16,22-tetraol

But-2-yne-1,4-diol (1.70 g, 19.75 mmol, 2.5 eq.) and tetrabutylammoniumbromide (TBAB, 0.50 g, 1.58 mmol, 0.2 eq.) were taken in an Argonflushed 50 mL three neck round bottom flask. To this, was added 12 mLchlorobenzene and the mixture was heated to 110° C. until the reagentswere completely dissolved. A solution of 1,4-butanediol diglycidyl ether(1.60 g, 7.91 mmol, 1.0 eq.) in 10 mL chlorobenzene was then added tothe above mixture with the help of a syringe and the reaction was heatedovernight. Flash chromatography of the crude (silica gel,EtOAc/MeOH=96:4) gave the pure product (R_(f)=0.22 in EtOAc/MeOH=96:4)as a colourless oil (1.84 g, 62%).

¹H NMR (300 MHz, CD₃CN): δ=4.18 (s, 8H), 3.82 (br.s, 2H), 3.51 (dd,J=9.9 Hz, 4.4 Hz, 2H), 3.46-3.32 (m, 12H), 3.17 (br.s, 2H), 1.61-1.57(m, 4H). ¹³C NMR (75 MHz, CD₃CN): δ=86.3 (2C), 81.5 (2C), 72.9 (2C),72.2 (2C), 71.8 (2C), 70.1 (2C), 59.3(2C), 50.6(2C), 27.1 (2C). IR(film): v=3392, 2919, 2867, 1445, 1356, 1229, 1122, 1090, 1016, 873, 597cm⁻¹. HRMS (ESI): m/z calcd. for C₁₈H₃₀O₈: 397.1833 [M+Na⁺]; found:397.1832.

4,4′-((((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(2-hydroxypropane-3,1-diyl))bis(oxy))bis(but-2-yn-1-ol)

But-2-yne-1,4-diol (2.15 g, 24.96 mmol, 2.5 eq.) and tetrabutylammoniumbromide (TBAB, 0.65 g, 1.99 mmol, 0.2 eq.) were taken in an Argonflushed 50 mL three neck round bottom flask. To this, was added 15 mLchlorobenzene and the mixture was heated to 110° C. until the reagentswere completely dissolved. A solution of bisphenol-A-diglycidyl ether(3.40 g, 9.98 mmol, 1.0 eq.) in 15 mL chlorobenzene was then added tothe above mixture with the help of a syringe and the reaction was heatedovernight. Flash chromatography of the crude (silica gel,EtOAc/MeOH=98:2) gave the pure product (R_(f)=0.54 in EtOAc/MeOH=98:2)as a colourless oil (3.84 g, 75%).

¹H NMR (400 MHz, CD₃CN): δ=7.14 (d, J=8.8 Hz, 4H), 6.83 (d, J=8.8 Hz,4H), 4.18 (m, 8H), 3.99 (dd, J=18.8 Hz, 13.4 Hz, 4H), 3.90 (dd, J=9.7Hz, 6.0 Hz, 2H), 3.58 (ddd, J=15.7 Hz, 9.9 Hz, 5.2 Hz, 4H), 3.27 (d,J=4.9 Hz, 2H), 3.16 (t, J=5.8 Hz, 2H), 1.61 (s, 6H). ¹³C NMR (101 MHz,CD₃CN): δ=157.7 (2C), 144.3 (2C), 128.6 (4C), 114.9 (4C), 86.4 (2C),81.4 (2C), 71.8 (2C), 70.3 (2C), 69.7 (2C), 59.3 (2C), 50.6 (2C), 42.3,31.2 (2C). IR (film): v=3379, 2931, 2871, 1607, 1510, 1461, 1361, 1297,1248, 1184, 1124, 1087, 1013, 830, 575 cm⁻¹. HRMS (ESI): m/z calcd. forC₂₉H₃₆NaO₈: 535.2305 [M+Na⁺]; found: 535.2302.

General Procedure for the Carboxylative Cyclisation of 1,4-butynediolDerivatives

A steel autoclave was charged with Alkynol (5.0 mmol), AgOAc (5 mol %),Ligand A (5 mol %) and solvent (10 mL) under atmospheric conditions. Thereaction mixture was pressurized with CO₂ (20 bar) and stirred at roomtemperature for 18 h. Then CO₂ overpressure was carefully released andsolvent evaporated. The resulting crude mixture was purified by flashcolumn chromatograph.

(4Z,4′Z)-4,4′-(((((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(2-hydroxypropane-3,1-diyl))bis(oxy))bis(ethan-2-yl-1-ylidene))bis(1,3-dioxolan-2-one)

Colorless oil, 545 mg (93%) for a reaction scale of 0.97 mmol. R_(f)(EtOAc)=0.59. ¹H NMR (300 MHz, CDCl₃): δ=7.16-7.10 (m, 4H), 6.84-6.78(m, 4H), 5.01-4.88 (m, 6H), 4.23-4.21 (m, 2H), 4.20-4.18 (m, 2H),4.17-4.09 (m, 2H), 4.03-3.95 (m, 4H), 3.67-3.56 (m, 4H), 2.52 (br.s,2H), 1.63 (s, 6H). ¹³C NMR (75 MHz, CDCl₃): δ=156.4 (2C), 152.3 (2C),144.4 (2C), 143.8 (2C), 127.9 (4C), 114.0 (4C), 99.9 (2C), 71.3 (2C),69.2 (2C), 68.9 (2C), 67.4 (2C), 64.5 (2C), 41.8, 31.1 (2C). IR (film):v=3446, 2964, 2930, 2873, 1832 (C═O), 1724, 1608, 1510, 1463, 1382,1297, 1249, 1127, 831, 724 cm⁻¹. HRMS (ESI): m/z calcd. for C₃₁H₃₆O₁₂:623.2099 [M+Na⁺]; found: 623.2101. Anal. Calcd. for C₃₁H₃₆O₁₂: C 61.99%,H 6.04%, Found: C 61.96%, H 6.06%.

(4Z,4′Z)-4,4′-(5,14-dihydroxy-3,7,12,16-tetraoxaoctadecane-1,18-diylidene)bis(1,3-dioxolan-2-one)

Colorless liquid, 426 mg (95%) for a reaction scale of 0.97 mmol. R_(f)(EtOAc/MeCN 96:4)=0.19. ¹H NMR (400 MHz, CDCl₃): δ=5.03-5.02 (m, 4H),4.95 (tt, J=7.1 Hz, 2.0 Hz, 2H), 4.20 (t, J=1.4 Hz, 2H), 4.18 (t, J=1.3Hz, 2H), 3.98-3.91 (m, 2H), 3.55-3.41 (m, 12H), 2.68 (br.s, 1H),1.67-1.63 (m, 4H). ¹³C NMR (100 MHz, CDCl₃): δ=152.4 (2C), 144.3 (2C),100.1 (2C), 71.9 (2C), 71.7 (2C), 71.4 (2C), 69.6 (2C), 67.5 (2C), 64.4(2C), 26.4 (2C). IR (film): v=3441, 2919, 2870, 1832 (C═O), 1724, 1465,1381, 1297, 1214, 1103, 1044, 958, 916, 874, 766, 734, 574 cm⁻¹. HRMS(ESI): m/z calcd. for C₂₀H₃₀O₁₂: 485.1629 [M+Na⁺]; found: 485.1627.Anal. Calcd. for C₂₀H₃₀O₁₂: C 51.95%, H 6.54%, Found: C 51.97%, H 6.54%.

1. A compound of formula (I),

wherein n is 2, 3 or 4, m is 0, Z is a single bond or a divalent organicgroup which is —CH₂—, —C(═O)—, —C(═O)—O—, or —C(═O)—N(R⁵)—, A is apoly(meth) acrylate, polyester, polyurethane, polyether, polyamide,polycarbonate, polyolefin, or a n-valent organic group derived from aC₁-C₁₂-alkane, saturated C₃-C₆₀-heterocycle, aromaticC₆-C₄₀-hydrocarbon, C₂-C₄₀-heteroarene, or C₇-C₃₀-arylalkane, wherein,in each member of the n-valent organic group, one or more hydrogen atomsis optionally substituted by halogen, —OH, —NR⁶ ₂, or —CN and one ormore CH₂-groups is optionally substituted by —O—, —S—, —N(R⁶)—, PO₂—,—SO₂—, —C(═O)—, —C(═O)—O—, or —C(═O)—N(R⁵)—, R⁵ being hydrogen, C₁-C₄alkyl, or phenyl, and R⁶ being C₁-C₄ hydrogen, alkyl, or phenyl.
 2. Thecompound of claim 1, wherein n is 2 or
 3. 3. The compound of claim 1,wherein n is
 2. 4. The compound of claim 1, wherein R⁵ is present and isH.
 5. A process for preparing the compound of claim 1, the processcomprising: (a) reacting a 4-oxy-but-2-yn-1-ol derivative of formula(II)

wherein R¹, R², R³, Z, A, X, n, and m have the same meaning as informula (I), with carbon dioxide in the presence of at least onetransition metal catalyst TMC1 comprising a transition metal of groups10, 11 of 12 of the IUPAC periodic table of the elements and at leastone bulky ligand of formula (III) and/or formula (IV)

wherein D is P, As, or Sb, R⁷ is an organic radical comprising 1 to 40carbon atoms, R⁸ and R⁹ are independently an organic radical comprising1 to 40 carbon atoms, R¹⁰ is an organic radical comprising 1 to 40carbon atoms or is identical to R⁷, and Z is —CR¹²═CR¹³—, —CR¹²═N—,—CR¹²R¹⁴—CR¹³R¹⁵—, or —CR¹²R¹⁴—CR¹³R¹⁵—CR¹⁶R¹⁷—, R¹², R¹³, R¹⁴, R¹⁵,R¹⁶, and R¹⁷ being independently H, a moiety as defined for R¹⁰, or twoadjacent radicals R¹² and R¹³ and/or R¹⁵ and R¹⁶ together with atomsconnecting them form a monocyclic or polycyclic ring system comprising 4to 40 carbon atoms and optionally Si, Ge, N, P, O, or S.
 6. A processfor preparing the compound of claim 1, the process comprising: (b)reacting an alcohol of formula (VI)

with a compound of formula (VII)

wherein R¹, R², R³, A, X, n, and m have the same meaning as in formulaI, J is a divalent organic group comprising 1 to 100 carbon atoms, Q isa functional group capable of reacting with the hydroxy group of thealcohol of formula (VI) in an addition reaction to form an —O-Q(-H)-Aunit or Q is a leaving group substituted by the oxygen of the hydroxygroup of the alcohol of formula (VI) to form H-Q, and o is 0 or
 1. 7.The process of claim 5, wherein Q is —N═C═O, 2-oxiranyl, —C═N—, halide,organic sulfonate, OH, R^(a)C(═O)O, R^(a)O, or imidazole, and whereinR^(a) is C₁-C₄ alkyl or phenyl.
 8. The process of claim 5, wherein Q isCl, Br, or I
 9. The process of claim 5, wherein Q is tosylate, mesylate,triflate, or nonaflate.
 10. A two-component composition, comprising: thecompound of claim 1, wherein n is 2, 3, 4, 5, or 6, and m is 0; and amultifunctional hardener comprising at least two functional groups whichare independently a primary amine, secondary amine, hydroxy group,phosphine, phosphonate, carboxyl group, or mercaptan.
 11. A polymer oroligomer, comprising, in reacted form: the compound of claim 1 used asan intermediate, crosslinker, or monomer.
 12. The polymer of claim 11,comprising, in reacted form, the compound as a monomer.
 13. The polymerof claim 12, which is a reaction product of the compound of claim 1 andone or more multi-functional compounds comprising at least twofunctional groups which are independently a primary amine, secondaryamine, hydroxy groups, carboxylate, phosphine, phosphonate, ofmercaptan.
 14. The polymer of claim 13, wherein the multi-functionalcompound comprises a polyol, polyacid, polyamine, and/orpolyamido-amine.
 15. A two-component composition, comprising: thepolymer of claims 12; and a multifunctional hardener comprising at leasttwo functional groups which are independently a primary amine, secondaryamine, hydroxy group, phosphine, phosphonate, or mercaptan.
 16. Acomponent of an adhesive and/or sealant, comprising: the compound ofclaim 1, wherein the adhesive and/or sealant is suitable for a rigid andflexible part, made from metal, plastic, paper, paperboard, textile,glass, leather, wood, and/or inorganic material.
 17. A coating,comprising: the compound of claim 1, wherein the coating is suitable fora rigid and flexible substrate, made from metal, plastic, paper,paperboard, textile, glass, leather, wood, and/or inorganic material.18. A binder suitable for fibers, particles, and/or pigments, the bindercomprising the compound of formula
 1. 19. A polyunsaturated compound,comprising, in reacted form: the compound of claim 1, and a(oligo/poly)-functional nucleophile, reacted with the compound offormula (I).